WO2020040042A1 - Chemical solution and chemical solution container - 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

Chemical solution, chemical solution container

The present invention relates to a drug solution and a drug solution container.

In the manufacture of a semiconductor device by a wiring forming process including photolithography, a pre-wet solution, a resist solution (composition for forming a resist film), a developing solution, a rinsing solution, a stripping solution, and chemical mechanical polishing (CMP). A chemical solution containing water and / or an organic solvent is used as a slurry, a cleaning solution after CMP, or a diluent thereof.
In recent years, miniaturization of patterns has been progressing due to the progress of photolithography technology. As a method of pattern miniaturization, pattern formation using an ultraviolet light, a KrF excimer laser, an ArF excimer laser, EUV (extreme ultraviolet light), or the like as an exposure light source has been attempted.
With the miniaturization of the pattern to be formed, the above-mentioned chemical solution used in this process is required to have further defect suppressing properties.

Patent Literature 1 discloses, as a conventional chemical solution used for pattern formation, “a method for producing an organic treatment solution for patterning a chemically amplified resist film capable of reducing generation of particles in a pattern formation technique (paragraph [0010]). ) "Is disclosed.

JP-A-2015-08122

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 need for a chemical solution that is less likely to cause defects.
It is an object of the present invention to provide a chemical solution in which metal residue defects are less likely to occur when the chemical solution is 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 drug solution container.

The present inventors have conducted intensive studies to solve the above-described problems, and as a result, have found that the above-described 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,
To the content of titanium ions, the mass ratio of the content of titanium oxide particles is ¹⁰ 0 to ^{10 12,} the drug solution.
(2) The chemical according to (1), wherein the content of titanium ions is 0.10 to 100 mass ppt based on the total mass of the chemical.
(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 drug solution according to any one of (1) to (3), wherein the proportion of particles having a particle size of 0.5 to 17 nm among the titanium oxide particles is from 60% by mass to 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 mass ppt 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 based on 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 the 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,
To the content of iron ions, the mass ratio of the content of the iron oxide particles is ¹⁰ 0 to ^{10 12,} the drug solution according to any one of (1) to (7).
(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 based on 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 a proportion of the 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,
To the content of aluminum ions, the mass ratio of the content of aluminum oxide particles is ¹⁰ 0 to ^{10 12,} the drug solution according to any one of (1) to (11).
(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 the 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,
To the content of copper ions, the mass ratio of the content of copper oxide particles is ¹⁰ 0 to ^{10 12,} the drug solution according to any one of (1) to (14).
(16) It further contains organic impurities,
The chemical solution according to any one of (1) to (15), wherein the content of the organic impurities is 1,000 to 100,000 mass ppt based on the total mass of the chemical solution.
(17) The drug solution according to any one of (1) to (16), wherein the content of water with respect to the total weight of the drug 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 It made containing one or more selected from the group drug solution according to any one of (1) to (17).
(19) A drug solution container comprising a container and the drug solution according to any one of (1) to (18) stored in the container.

ADVANTAGE OF THE INVENTION According to this invention, when contacting with a silicon substrate or a silicon substrate with a silicon oxide film, the chemical liquid which a metal residue defect does not generate easily can be provided.
Further, according to the present invention, a drug solution container can be provided.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In addition, in this specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
In the present invention, “ppm” means “parts-per-million (10 ⁻⁶ )”, “ppb” means “parts-per-billion (10 ⁻⁹ )”, and “ppt” means “Parts-per-trillion (10 ⁻¹² )” means “parts-per-quadrillion (10 ⁻¹⁵ )”.
Further, in the notation of the group (atom group) in the present invention, the notation that does not indicate substitution or unsubstitution means a group containing a substituent together with a group having no substituent within a range not impairing the effect of the present invention. Is also included. For example, the “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). This is the same for each compound.
Further, “radiation” in the present invention means, for example, far ultraviolet rays, extreme ultraviolet (EUV), X-rays, or electron beams. 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 or EUV, but also drawing with particle beams such as electron beams or ion beams.

Although the mechanism by which the above-mentioned problem is solved by the chemical solution of the present invention is not always clear, the present inventors presume the mechanism as follows. In addition, the following mechanism is speculation, and even when the effect of the present invention is obtained by a different mechanism, it is included in the scope of the present invention.
The present inventors, when the chemical solution contains titanium oxide particles and titanium ions, the silicon substrate or silicon substrate with a silicon oxide film (hereinafter referred to as these) by the mass ratio (mass of titanium oxide particles / mass of oxide ions). It has been found that the likelihood of occurrence of metal residue defects (residues derived from metal components) on the “specific substrate” is different. More specifically, when the mass ratio is too large, in other words, when the ratio of the titanium oxide particles is too large, it is considered that metal residue defects derived from the titanium oxide particles tend to increase on a specific substrate. In addition, when the mass ratio is too small, in other words, when the ratio of titanium ions is too large, the oxidation-reduction reaction easily proceeds with other metal ions which are more noble than titanium ions, and particles of other metals. It is considered that (for example, oxide particles of another metal) increase and metal residue defects easily increase on a 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, with respect to the content of titanium ions, the content of titanium oxide particles. mass ratio is ¹⁰ 0 to ^{10 12.}
Hereinafter, the components contained in the chemical solution of the present invention will be described in detail.

<Organic solvent>
The chemical solution of the present invention (hereinafter, also simply referred to as “chemical solution”) contains an organic solvent.
In the present specification, an organic solvent is intended to mean a liquid organic compound contained at a content exceeding 10,000 mass ppm per component with respect to the total mass of the chemical solution. That is, in this specification, a liquid organic compound contained in an amount exceeding 10,000 ppm by mass with respect to the total mass of the chemical solution corresponds to an organic solvent.
In addition, in the present specification, the term “liquid” means a liquid at 25 ° C. and 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 based on the total mass of the chemical solution. Preferably, it is more than 99.95% by mass. 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.

種類 The type of the organic solvent is not particularly limited, and a known organic solvent can be used. Examples of the organic solvent include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), and monoketone compound optionally having a ring. (Preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate, dialkyl sulfoxide, cyclic sulfone, dialkyl ether, monohydric alcohol, glycol, alkyl acetate, and N-alkylpyrrolidone. .

Examples of the organic solvent include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), propylene carbonate (PC), isopropanol (IPA), and 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- Methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, sulfolane, cycloheptanone, Heptanone, butyl butyrate, isobutyl isobutyrate, isoamyl ether, and one or more selected from the group consisting of undecane is preferred.
Examples of using two or more organic solvents include a combination of PGMEA and PGME, and a combination of PGMEA and PC.
In addition, the kind and content of the organic solvent in the chemical solution can be measured using a gas chromatograph mass spectrometer.

<Metal components>
The chemical solution contains a metal component.
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 only need to include metal atoms, and examples thereof include metal oxide particles, metal nitride particles, and metal particles. The metal particles mean particles made of metal.

The metal component contained in the chemical solution contains titanium oxide particles and titanium ions.
To the content of titanium ions, a mass ratio of 10 0 ^to 10 ¹² of the content of titanium oxide particles, on a silicon substrate or a silicon oxide film, and more hardly generates points composites residue defects residual metal defects or later in, the mass ratio is ^preferably from 10 1 to ^{10 10,} more preferably from 10 2 to ^{10 10,} more preferably 10 3 to 10 ^8, more 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, based on the total mass of the chemical solution, in that metal residue defects or composite residue defects described later are less likely to occur on a silicon substrate or a silicon oxide film. , And more preferably 1.0 to 70 mass ppt.

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. Among them, on the silicon substrate or on the silicon oxide film, metal residue defects or composite residue defects described below are less likely to occur, the content of the titanium oxide particles is relative to the content of the titanium component in the metal component. It is preferably from 5% by mass to less than 99% by mass, more preferably from 30 to 90% by mass.
The titanium component is a component containing a titanium atom, 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.
The titanium-containing particles only need to contain titanium atoms, and examples thereof include titanium oxide particles, titanium nitride particles, and titanium particles. The titanium particles mean particles made of titanium metal.

割 合 Of the titanium oxide particles, the ratio 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 titanium oxide particles is 60%, because metal residue defects or composite residue defects described later are less likely to occur on a silicon substrate or a silicon oxide film. It is preferably at least 80% by mass and less than 98% by mass, more preferably from 60 to 95% by mass.

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 mass ppt based on 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 solution in that metal residue defects or composite residue defects described later are less likely to occur on a silicon substrate or a silicon oxide film. , And more preferably 1.0 to 90 mass ppt.

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, on the silicon substrate or on the silicon oxide film, metal residue defects or composite residue defects described below are less likely to occur, the content of the iron oxide particles is relative to the content of the iron component in the metal component. It is preferably from 5% by mass to less than 99% by mass, more preferably from 10 to 95% by mass.
The iron component is a component containing an iron atom, and includes iron-containing particles and iron ions. For example, when referring to the iron component content, it indicates the total content of the 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. The iron particles mean particles made of metallic iron.

割 合 Of the iron oxide particles, the ratio 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. Among them, the ratio of particles having a particle diameter of 0.5 to 17 nm among iron oxide particles is 60, because metal residue defects or composite residue defects described later are less likely to be formed on a silicon substrate or a silicon oxide film. It is preferably at least 80% by mass and less than 98% by mass, more preferably from 60 to 95% by mass.

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 . Among them, the mass ratio is preferably from 10 ⁰ to 10 ¹² , more preferably from 10 ² to 10 ¹⁰ , in that metal residue defects or composite residue defects described later are less likely to be formed on the silicon substrate or the silicon oxide film. And 10 ³ to 10 ⁸ are more preferable, and 10 ³ to 10 ⁷ is particularly preferable.

The metal component contained in the chemical solution may contain aluminum ions.
The content of the aluminum ion is not particularly limited, and is often 0.01 to 200 mass ppt 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 solution in that metal residue defects or composite residue defects described later are less likely to occur on a silicon substrate or a silicon oxide film. , And more preferably 1.0 to 90 mass ppt.

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. Among them, on the silicon substrate or on the silicon oxide film, metal residue defects or composite residue defects described below are less likely to occur, the content of the aluminum oxide particles is relative to the content of the aluminum component in the metal component. It is preferably from 5% by mass to less than 99% by mass, more preferably from 10 to 95% by mass.
The aluminum component is a component containing an aluminum atom, and includes aluminum-containing particles and aluminum ions. For example, when referring to the content of the aluminum component, it indicates 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. The aluminum particles mean particles made of metallic aluminum.

割 合 Of the aluminum oxide particles, the ratio 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 aluminum oxide particles is 60%, because metal residue defects or composite residue defects described later are less likely to be formed on a silicon substrate or a silicon oxide film. It is preferably at least 80% by mass and less than 98% by mass, more preferably from 60 to 95% by 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, and is often 10 ⁻² to 10 ¹⁴ . Among them, the mass ratio is preferably from 10 ⁰ to 10 ¹² , more preferably from 10 ² to 10 ¹⁰ , in that metal residue defects or composite residue defects described later are less likely to be formed on the silicon substrate or the silicon oxide film. And 10 ³ to 10 ⁸ are more preferable, and 10 ³ to 10 ⁷ is particularly preferable.

The metal component contained in the chemical solution may contain components of other metal atoms than those described above.
Other metal atoms include, for example, 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. Among them, on the silicon substrate or on the silicon oxide film, metal residue defects or composite residue defects described below are less likely to occur, the content of the copper oxide particles is relative to the content of the copper component in the metal component. It is preferably from 5% by mass to less than 99% by mass, more preferably from 10 to 95% by mass.
The copper component is a component containing a copper atom, and includes copper-containing particles and copper ions. For example, when referring to the content of the copper component, it indicates 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. The copper particles mean particles made of metallic copper.

割 合 Of the copper oxide particles, the ratio of the 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. Among them, the proportion of particles having a particle diameter of 0.5 to 17 nm among copper oxide particles is 60%, because metal residue defects or composite residue defects described later are less likely to be formed on a silicon substrate or a silicon oxide film. It is preferably at least 80% by mass and less than 98% by mass, more preferably from 60 to 95% by mass.

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 . Among them, the mass ratio is preferably from 10 ⁰ to 10 ¹² , more preferably from 10 ² to 10 ¹⁰ , in that metal residue defects or composite residue defects described later are less likely to be formed on the silicon substrate or the silicon oxide film. And 10 ³ to 10 ⁸ are more preferable, and 10 ³ to 10 ⁷ is particularly preferable.

The metal component may be a metal component inevitably included in each component (raw material) included in the chemical solution, or may be a metal component inevitably included in 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, the metal residue defect or the composite residue defect described below is less likely to be formed on the silicon substrate or the silicon oxide film, and thus the content is 10 to 500,000 mass% based on the total mass of the chemical solution. ppt is preferred.

Note that the types and contents of metal ions and metal-containing particles in a chemical solution can be measured by an SP-ICP-MS method (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry).
Here, the SP-ICP-MS method uses an apparatus similar to a 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 by commercially available software.
In the ICP-MS method, the content of a metal component to be measured is measured regardless of its existing form. Therefore, the total mass of the metal-containing particles to be measured and the metal ions is determined as the content of the metal component.

On the other hand, in the SP-ICP-MS method, the content of metal-containing particles can be measured. Therefore, by subtracting the content of the metal-containing particles from the content of the metal component in the sample, the content of the metal ion in the sample can be calculated.
As an apparatus of the SP-ICP-MS method, for example, Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, option # 200 for semiconductor analysis, option # 200) manufactured by Agilent Technologies, Inc. is described in Examples. Can be measured by the following method. As an apparatus other than the above, in addition to NexION350S manufactured by PerkinElmer, Agilent 8900 manufactured by Agilent Technologies can be used.

In addition, since the 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 converted value of the 20 nm particles from SNP-ICP-MS is used for the count. Here, 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, if 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 is calculated as 1000 (100 × 10) in the chemical based on 10 times the converted value. The number of particles having a size of 10 nm or less in the present invention is estimated by this conversion method regardless of the type of metal.

<Organic impurities>
The chemical may contain organic impurities.
The content of the organic impurities in the chemical solution is not particularly limited, but is preferably from 1,000 to 100,000 mass ppt based on the total mass of the chemical solution from the viewpoint that stain-like residue defects described later are less likely to be formed on the silicon substrate.
Note that the organic impurity is an organic compound different from the organic solvent, and means an organic compound contained at a content of 10000 ppm by mass or less based on the total mass of the organic solvent. That is, in the present specification, an organic compound contained at a content of 10,000 mass ppm or less based on the total mass of the organic solvent corresponds to an organic impurity and does not correspond to an organic solvent.
Organic impurities are often mixed with or added to a chemical solution during the process of refining a substance to be purified to obtain a chemical solution. Examples of such organic impurities include a plasticizer, an antioxidant, and a compound derived from these (typically, a decomposition product).

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

水 の The content of water in the chemical is not particularly limited, but is preferably 2.0% by mass or less, more preferably 500% by mass or less, based on the total mass of the chemical. The lower limit is not particularly limited, but 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.

<Use of chemicals>
The chemical solution of the present invention is preferably used for manufacturing a semiconductor device. Especially, 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, and a peeling process, an organic material is processed after each process or before moving to the next process. Specifically, it is suitably used as a pre-wet liquid, a developing liquid, a rinsing liquid, a polishing liquid or the like.
In addition, the chemical solution may be used as a diluting solution of the resin contained in the resist film forming composition (in other words, a solvent).

In addition, the above-mentioned chemical solution can be used for other uses other than the production of semiconductor devices, and can also be used as a developer and a rinse for polyimide, a resist for sensors, a resist for lenses, and the like.
Further, the above chemical solution can be used as a solvent for medical use or cleaning use. For example, it can be suitably used for cleaning pipes, containers, and substrates (for example, wafers and glass).
As the above-mentioned cleaning use, it is also preferable to use as a cleaning liquid (a pipe cleaning liquid and a container cleaning liquid, etc.) for cleaning pipes, containers, and the like that come into contact with a liquid such as the above-mentioned pre-wet liquid.

Among them, the chemical solution is suitably used for a pre-wet solution, a developing solution, a rinsing solution, a polishing solution, and a composition for forming a resist film. Above all, when applied to a pre-wet liquid, a developing liquid and a rinsing liquid, more excellent effects are exhibited. In particular, when the present invention is applied to a pre-wet liquid, a developing liquid and a rinsing liquid when the exposure light source is EUV, a more excellent effect is exhibited. Further, even when the present invention is applied to a pipe cleaning liquid used for pipes used for transferring these liquids, more excellent effects are exhibited.

<Chemical liquid manufacturing method>
The method for producing the chemical solution is not particularly limited, and a known production method can be used. Above all, in that a chemical solution exhibiting a better effect of the present invention can be obtained, the method for producing a chemical solution has a filtration step of filtering a substance to be purified containing an organic solvent using a filter to obtain a chemical solution. preferable.

(4) The material to be purified used in the filtration step may be procured by purchasing or the like, or may be obtained by reacting the raw materials. It is preferable that the material to be purified has a low impurity content. Examples of such a commercially available product to be purified include a commercially available product called “high-purity grade product”.

There is no particular limitation on the method of obtaining the object to be purified (typically, the object to be purified containing an organic solvent) by reacting the raw materials, and a known method can be used. For example, there is a method in which one or more raw materials are reacted in the presence of a catalyst to obtain an organic solvent.
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 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 give IPA (isopropyl). alcohol) by reacting lactic acid and ethanol to obtain lactic acid. And the like; a method of obtaining a chill.

(Filtration process)
The method for producing a drug solution of the present invention preferably includes a filtration step of filtering the above-mentioned substance to be purified using a filter to obtain a drug solution. The method of filtering the object to be purified using a filter is not particularly limited, and the object to be purified is passed through a filter unit having a housing and a filter cartridge housed in the housing with or without pressurization ( Is preferable.

-Pore size of filter The pore size of the filter is not particularly limited, and a filter having a pore size usually used for filtering a substance to be purified can be used. Above all, the pore diameter of the filter is preferably 200 nm or less, more preferably 20 nm or less, still more preferably 10 nm or less, and more preferably 5 nm or less, in that the number of particles (metal particles and the like) contained in the drug solution can be easily controlled in a desired range. Is particularly preferred. The lower limit is not particularly limited, but is generally preferably 1 nm or more from the viewpoint of productivity.
In addition, in this specification, the pore diameter of a filter means the pore diameter determined by the bubble point of isopropanol (IPA).

It is preferable that the pore diameter of the filter be 5.0 nm or less, since the number of particles contained in the drug solution can be more easily controlled. Hereinafter, a filter having a pore size of 5.0 nm or less is also referred to as a “micropore size filter”.
The micropore size filter may be used alone, or may be used with a filter having another pore size. Among them, it is preferable to use a filter having a larger pore diameter from the viewpoint of better productivity. That is, when two or more filters are used, it is preferable that at least one filter has a pore diameter of 5.0 nm or less. In this case, if the object to be purified, which has been filtered through a filter having a larger pore diameter in advance, is passed through a micropore size filter, clogging of the micropore size filter can be prevented.
That is, when one filter is used, the pore diameter of the filter is preferably 5.0 nm or less, and when two or more filters are used, the pore diameter of the filter having the smallest pore diameter is 5.0 nm. The following is preferred.

形態 The form in which two or more types of filters having different pore diameters are sequentially used is not particularly limited, and examples thereof include a method of sequentially arranging the above-described filter units along a pipe through which a substance to be purified is transferred. At this time, when trying to keep the flow rate per unit time of the object to be purified as a whole pipe line, a larger pressure may be applied to a filter having a smaller pore size as compared with a filter having a larger pore size. . In this case, a pressure regulating valve, a damper, etc. are arranged between the filters to make the pressure applied to the filter having a small pore diameter constant, or a filter unit containing the same filter is placed along the pipeline. It is preferable to increase the filtration area by arranging them in parallel. This makes it possible to more stably control the number of particles in the chemical solution.

-Material of the filter The material of the filter is not particularly limited, and known materials for the filter can be used. Specifically, when it is a resin, polyamide such as nylon (for example, 6-nylon and 6,6-nylon); polyolefin such as polyethylene and polypropylene; polystyrene; polyimide; polyamideimide; Polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylene propene copolymer, ethylene / tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride Fluorocarbon; polyvinyl alcohol; polyester; cellulose; cellulose acetate and the like.
Among them, nylon (especially, 6,6-nylon is preferred), polyolefin (especially, polyethylene is preferred), and polyolefin are preferred in that they have better solvent resistance and the resulting chemical has more excellent defect suppression performance. At least one selected from the group consisting of (meth) acrylate and polyfluorocarbon (among others, polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkane (PFA) is preferable) is preferable. These polymers can be used alone or in combination of two or more.
In addition to the resin, diatomaceous earth, glass, and the like may be used.
In addition, a polymer (eg, nylon grafted UPE) obtained by graft copolymerizing a polyamide (eg, nylon-6 or nylon-6,6, etc.) with a polyolefin (eg, UPE (ultra high molecular weight polyethylene) described below) is used as a filter. Material.

フ ィ ル タ ー The filter may be a surface-treated filter. The method for surface treatment is not particularly limited, and a known method can be used. Examples of the surface treatment method include chemical modification treatment, plasma treatment, hydrophobic treatment, coating, gas treatment, and sintering.

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

As the chemical modification treatment, a method of introducing an ion exchange group into a filter is preferable.
That is, a filter having an ion exchange group is preferable as the filter.
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 carboxy group, and a phosphate group, and examples of the anion exchange group include a quaternary ammonium group. No. The method for introducing the ion-exchange group into the filter is not particularly limited, and examples thereof include a method in which a compound containing an ion-exchange group and a polymerizable group is allowed to react with the filter and typically grafted.

方法 The method of introducing the ion exchange group is not particularly limited, but the filter is irradiated with ionizing radiation (α-ray, β-ray, γ-ray, X-ray, electron beam, etc.) to generate an active portion (radical). The filter after the irradiation is immersed in the monomer-containing solution, and the monomer is graft-polymerized on the filter. As a result, a polymer obtained by polymerizing this monomer is grafted on 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 an ion exchange group into the polymer.

フ ィ ル タ ー The filter may have a structure in which a woven or nonwoven fabric having an ion exchange group formed by a radiation graft polymerization method is combined with a conventional glass wool, woven or nonwoven fabric filter material.

When a filter having an ion exchange group is used, it is easy to control the contents of the metal-containing particles and metal ions in the chemical solution in a desired range. The material constituting the filter having an ion exchange group is not particularly limited, and examples thereof include a polyfluorocarbon and a material in which an ion exchange group is introduced into polyolefin, and a material in which an ion exchange group is introduced into polyfluorocarbon is more preferable.
Although the pore diameter of the filter having an ion exchange group is not particularly limited, it is preferably 1 to 30 nm, more preferably 5 to 20 nm. The filter having an ion-exchange group may also serve as the filter having the smallest pore diameter described above, or may be used separately from the filter having the smallest pore diameter. Above all, in the point that a drug solution exhibiting a superior effect of the present invention can be obtained, the filtration step uses a filter having an ion exchange group and a filter having no ion exchange group and having a minimum pore diameter. Is preferred.
The material of the filter having the smallest pore diameter already described is not particularly limited, but from the viewpoint of solvent resistance and the like, generally, polyfluorocarbon, and at least one selected from the group consisting of polyolefins are preferable. More preferred.

Therefore, as the filter used in the filtration step, two or more types of filters having different materials may be used. For example, polyolefins, polyfluorocarbons, polyamides, and filters made of materials having ion exchange groups introduced therein may be used. Two or more kinds selected from the group 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 object to be purified. In the present specification, the pore structure of a filter means a pore size distribution, a positional distribution of pores in a filter, and a shape of pores, and is typically controlled by a filter manufacturing method. It is possible.
For example, a porous film can be obtained by sintering a powder of a resin or the like, and a fiber film can be obtained by forming by a method such as electrospinning, electroblowing, and meltblowing. These have different pore structures.

A “porous membrane” refers to a membrane that retains components in an object to be purified, such as gels, particles, colloids, cells, and poly-oligomers, but a component that is substantially smaller than the pores passes through the pores. Means The retention of components in the object to be purified by the porous membrane may depend on operating conditions, such as surface velocity, use of surfactant, pH, and combinations thereof, and the pore size of the porous membrane, It may depend on the structure and the size of the particles to be removed, and the structure (hard particles or gels, etc.).

If the object to be purified contains negatively charged particles, a polyamide filter acts as a non-sieving membrane to remove such particles. Typical non-sieving membranes include, but are not limited to, nylon-6 membranes and nylon membranes such as nylon-6,6 membranes.
As used herein, "non-sieving" retention mechanism refers to retention caused by mechanisms such as filter pressure drop or interference, diffusion, and adsorption that are not related to pore size.

Non-sieve retention includes retention mechanisms, such as obstruction, diffusion, and adsorption, that remove particles to be removed from the object to be purified, regardless of the filter pressure drop or filter pore size. The adsorption of particles to the filter surface can be mediated, for example, by intermolecular van der Waals forces and electrostatic forces. An interfering effect occurs when particles traveling in a non-sieving membrane layer having a tortuous path are not turned 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 that the particles will collide with the filter media. If there is no repulsion between the particles and the filter, the non-sieve retention mechanism can be active.

UPE (ultra high molecular weight polyethylene) filters are typically sieved membranes. A sieve membrane means a membrane that mainly captures particles via a sieve holding mechanism, or a membrane that is optimized for capturing particles via a sieve holding mechanism.
Typical examples of sieving membranes include, but are not limited to, polytetrafluoroethylene (PTFE) membranes and UPE membranes.
Note that the “sieve holding mechanism” refers to holding the result due to the removal target particles being larger than the pore diameter of the porous membrane. The sieve retention is improved by forming a filter cake (agglomeration of the particles to be removed on the surface of the membrane). The filter cake effectively performs the function of a secondary filter.

材質 The material of the fiber membrane is not particularly limited as long as it is a polymer capable of forming the fiber membrane. Examples of the polymer include polyamide and the like. Examples of the polyamide include nylon 6, nylon 6,6, and the like. The polymer forming the fiber membrane may be poly (ether sulfone). When the fibrous membrane is on the primary side of the porous membrane, the surface energy of the fibrous membrane is preferably higher than the polymer which is the material of the porous membrane 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).

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

The pore structure of the porous membrane (for example, a porous membrane containing UPE, PTFE, or the like) is not particularly limited, and examples of the pore shape include a lace shape, a string shape, and a node shape. Can be
The distribution of pore sizes in the porous membrane and the distribution of positions in the membrane are not particularly limited. The size distribution may be smaller and the distribution position in the film may be symmetric. Further, the size distribution may be larger and the distribution position in the film may be asymmetric (the above film is also referred to as “asymmetric porous film”). In an asymmetric porous membrane, the size of the pores varies in the membrane, and typically the pore size increases from one surface of the membrane to the other surface of the membrane. At this time, the surface on the side with many pores having a large pore diameter is called “open side”, and the surface on the side with many pores with small pore diameter is also called “tight side”.
Examples of the asymmetric porous membrane include a membrane in which the size of pores is minimized at a certain position within the thickness of the membrane (this is also referred to as an “hourglass shape”).

If the primary side is made to have a larger-sized pore using the asymmetric porous membrane, in other words, if the primary side is made to be the open side, a pre-filtration effect can be produced.

The porous membrane may include thermoplastic polymers such as PESU (polyethersulfone), PFA (perfluoroalkoxyalkane, copolymer of ethylene tetrafluoride and perfluoroalkoxyalkane), polyamide, and polyolefin. , Polytetrafluoroethylene and the like.
Among them, ultrahigh molecular weight polyethylene is preferable as the material of the porous membrane. Ultra-high molecular weight polyethylene means a thermoplastic polyethylene having an extremely long chain, and preferably has a molecular weight of 1,000,000 or more, typically 2,000,000 to 6,000,000.

As a filter used in the filtration step, two or more types of filters having different pore structures may be used, or a filter of a porous membrane and a filter of 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.

Further, it is preferable that the filter is sufficiently washed before use.
When an unwashed filter (or a filter that has not been sufficiently washed) is used, impurities contained in the filter are likely to be brought into the chemical solution.

As described above, in the filtration step according to the embodiment of the present invention, at least one selected from the group consisting of a filter material, a pore diameter, and a pore structure passes the material to be purified through two or more types of different filters. And a multi-stage filtration step.
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 a plurality of filters of the same type.

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

The material of the liquid contacting portion of the purification device used in the filtration step (meaning the substance to be purified and the inner wall surface to which the chemical solution may come into contact) is not particularly limited, but non-metallic materials (fluorinated resin And the like, and at least one selected from the group consisting of electrolytically polished metal materials (such as stainless steel) (hereinafter, these are collectively referred to as “corrosion-resistant materials”). For example, the wetted part of a production tank is formed of a corrosion-resistant material, which means that the production tank itself is made of a corrosion-resistant material, or the inner wall of the production tank is coated with a corrosion-resistant material. No.

The nonmetallic material is not particularly limited, and a known material can be used.
Non-metallic materials include, for example, polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, and fluorine-based resin (for example, ethylene tetrafluoride resin, ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer resin, ethylene tetrafluoride -Propylene hexafluoride copolymer resin, ethylene tetrafluoride-ethylene copolymer resin, ethylene trifluoride-ethylene copolymer resin, vinylidene fluoride resin, ethylene trifluoride ethylene copolymer resin, and vinyl fluoride resin And the like, but not limited thereto.

The metal material is not particularly limited, and a known material can be used.
Examples of the metal material include a metal material in which the total content of chromium and nickel is more than 25% by mass based on the total mass of the metal material, and among them, 30% by mass or more is more preferable. 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 the metal material include stainless steel and a nickel-chromium alloy.

The stainless steel is not particularly limited, and a known stainless steel can be used. Among them, alloys containing nickel at 8% by mass or more are preferable, and austenitic stainless steels containing nickel at 8% by mass or more are 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 10% by mass, Cr content 16% by mass) and SUS316L (Ni content 12% by mass, Cr content 16% by mass) and the like.

The nickel-chromium alloy is not particularly limited, and a known nickel-chromium alloy can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75% by mass and a chromium content of 1 to 30% by mass is preferable.
Examples of the nickel-chromium alloy include Hastelloy (trade name, the same applies hereinafter), Monel (trade name, the same applies hereinafter), and Inconel (trade name, the same applies 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-276 22 (Ni content 61% by mass, Cr content 22% by mass).
Further, the nickel-chromium alloy may further contain boron, silicon, tungsten, molybdenum, copper, cobalt, and the like, if necessary, in addition to the above alloy.

方法 The method of electropolishing the 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 a chromium content in the matrix due to electrolytic polishing. Therefore, it is presumed that the use of a refining device in which the liquid contact portion is formed from a metal material which has been electropolished, makes it difficult for metal-containing particles to flow out into the object to be purified.
The metal material may be buffed. The buffing method is not particularly limited, and a known method can be used. The size of the abrasive grains used for the buffing finish is not particularly limited, but is preferably # 400 or less from the viewpoint that irregularities on the surface of the metal material tend to be smaller. The buff polishing is preferably performed before the electrolytic polishing.

(Other processes)
The method for producing a chemical solution may further include a step other than the filtration step. The steps other than the filtration step include, for example, a distillation step, a reaction step, and a charge removal step.

(Distillation process)
The distillation step is a step of distilling an object to be purified containing an organic solvent to obtain a distilled object to be purified. The method for distilling the object to be purified is not particularly limited, and a known method can be used. Typically, there is a method in which a distillation column is arranged on the primary side of a purification device provided for a filtration step, and a distilled product to be purified is introduced into a production tank.
At this time, the liquid contact portion of the distillation column is not particularly limited, but is preferably formed of the corrosion-resistant material described above.

(Reaction step)
The reaction step is a step of reacting the raw materials to produce a purified product containing an organic solvent as a reactant. The method for producing the object to be purified is not particularly limited, and a known method can be used. Typically, there is a method in which a reaction tank is arranged on the primary side of a production tank (or a distillation column) of a purification device provided for a filtration step, and a reactant is introduced into the production tank (or a distillation column).
At this time, the liquid contact portion of the production tank is not particularly limited, but is preferably formed of the corrosion-resistant material described above.

(Static elimination process)
The charge elimination step is a step of removing charges from the object to be purified to reduce the charged 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 charge removal method include a method of contacting the object to be purified with a conductive material.
The contact time for contacting the object to be purified with the conductive material is preferably from 0.001 to 60 seconds, more preferably from 0.001 to 1 second, even more preferably from 0.01 to 0.1 second. Examples of the conductive material include stainless steel, gold, platinum, diamond, and glassy carbon.
As a method of bringing the object to be purified into contact with the conductive material, for example, a method of arranging a grounded mesh made of a conductive material in a pipe and passing the object through the pipe is mentioned.

精製 Purification of the object to be purified is preferably performed in a clean room, in which the opening of the container, the cleaning of the container and the device, the storage of the solution, and the analysis are all performed. The clean room is preferably a clean room having a class 4 or higher cleanliness specified by International Standard ISO1464-1: 2015 specified by the International Organization for Standardization. Specifically, it is preferable to satisfy any one of ISO class 1, ISO class 2, ISO class 3, and ISO class 4, more preferably to satisfy ISO class 1 or ISO class 2, and to satisfy ISO class 1. Is more preferred.

(4) The storage temperature of the drug solution is not particularly limited, but the storage temperature is preferably 4 ° C. or higher from the viewpoint that impurities and the like contained in a small amount in the drug solution are less likely to be eluted and, as a result, a superior effect of the present invention can be obtained.

<Chemical container>
The drug solution produced by the above purification method may be stored in a container and stored until use.
A combination of such a container and a drug solution contained in the container is referred to as a drug solution container. The medicinal solution is taken out from the stored medicinal solution container and used.

As a container for storing the chemical solution, it is preferable that the container has a high degree of cleanness and a small amount of impurities eluted for use in semiconductor device manufacturing.
Specific examples of usable containers include, but are not limited to, “Clean Bottle” series manufactured by Aicello Chemical Co., Ltd. and “Pure Bottle” manufactured by Kodama Resin Kogyo.

As the container, a multi-layer bottle having a six-layer structure made of six kinds of resins or a seven-layer structure made of six kinds of resins is used for the purpose of preventing impurities from being mixed into the chemical solution (contamination). Is also preferred. Examples of these containers include those described in JP-A-2015-123351.

The liquid-contact part of this container may be a corrosion-resistant material (preferably, electropolished stainless steel or fluorine resin) or glass described above. It is preferable that 90% or more of the area of the liquid contact part is made of the above-mentioned material, and it is more preferable that all of the liquid contact part is made of the above-mentioned material from the viewpoint that the superior effects of the present invention can be obtained.

The porosity of the liquid medicine container in the container is preferably 2 to 80% by volume, more preferably 2 to 50% by volume, and still more preferably 5 to 30% by volume.
Note that the porosity is calculated according to equation (1).
Formula (1): Porosity = {1− (volume of drug solution in container / volume of container)} × 100
The container volume is synonymous with the internal volume (capacity) of the container.
By setting the porosity in this range, storage stability can be ensured by limiting contamination such as impurities.

本 Hereinafter, the present invention will be described in more detail with reference to Examples. The materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

In the preparation of the chemical solutions of the examples and comparative examples, handling of containers, preparation of chemical solutions, filling, storage, and analytical measurement were all performed in a clean room of a level satisfying ISO class 2 or 1.

(filter)
The following filters were used as filters.
-"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 purified>
The following organic solvents were used as substances to be purified for the production of the chemical solutions of the 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 The "raw material 1" to "raw material 8" in the table are organic solvents used in each Example and Comparative Examples purchased from the following manufacturers. Indicates that there is.
"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 containers were used as containers for storing the chemicals.
EP-SUS: a container whose wetted part is electropolished stainless steel PFA: a container whose wetted part is coated with perfluoroalkoxyalkane The filling rate of the chemical in each container is 95% by volume ( The porosity was 5% by volume).
The filling rate is determined by the following equation.
Filling rate = (volume of drug solution in container / volume of container in container) × 100

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

Next, the purified product purified by distillation is stored in a storage tank, and the purified product stored in the storage tank is passed through filters 1 to 5 shown in Table 1 in this order and filtered. Stored in tank.
Next, the object to be purified stored in the storage tank is filtered through the filters 6 to 7 shown in Table 1, and the object to be purified after being filtered through the filter 7 is circulated upstream of the filter 6, and then filtered again. A circulating filtration process of filtering at 6 to 7 was performed.
After the circulation filtration treatment, the drug solution was stored in the container.
In Examples 85 to 88, water was added to the chemical so that the water content became a predetermined value.

In the above-described series of refining processes, the liquid contact parts of various devices (for example, distillation towers, pipes, storage tanks, etc.) with which the object to be purified comes into contact were made of electropolished stainless steel.

(4) The content of the organic component and the metal component in the chemical solution was measured by the method 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 equipment was used.
・ Manufacturer: PerkinElmer
・ Model: NexION350S
The following analysis software was used for the analysis.
・ Syngisix nano application module dedicated to “SP-ICP-MS” ・ Syngisix for ICP-MS software However, since the metal-containing particles of 10 nm or less cannot be measured by SP-ICP-MS, the above-mentioned specific method was used.

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

<Test>
(Pre-wet liquid or rinse liquid)
By the method described below, the defect suppression property of the manufactured chemical solution when used as a pre-wet solution or a rinse solution was evaluated.
First, a chemical solution is spin-discharged onto a silicon substrate having a diameter of 300 mm or a silicon substrate having a silicon oxide film having a diameter of 300 mm (a silicon substrate whose surface is covered with a silicon oxide film). Then, 0.5 cc of each chemical solution was discharged. Thereafter, the substrate was spin-dried. Next, using a wafer inspection apparatus “SP-5” manufactured by KLA-Tencor, the number of defects present on the substrate after the application of the chemical was measured (this is referred to as a measured value).
Next, using EDAX (energy-dispersive X-ray spectroscopy), the types of defects were classified into metal residue defects, composite residue defects, and spot residue defects. The metal residue defect is a residue derived from a metal component, the composite residue defect is a residue derived from a composite of an organic substance and a metal component, and the stain residue defect is a residue derived from an organic substance.
If both the “metal residue on Si” and the “metal residue on SiO ₂ ” are “D” or more, they are suitably used as a pre-wet liquid or a rinsing liquid.

<Individual evaluation (metal residue defect, composite residue defect, spot residue defect)>
A: The number of corresponding defects was 20 / substrate or less.
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)
The following method was used to evaluate the case where the manufactured chemical was used as a developer.
First, a resist pattern was formed by the following operation.
An actinic ray-sensitive or radiation-sensitive resin composition described below is applied to a silicon substrate having a diameter of 300 mm or a silicon substrate having a silicon oxide film having a diameter of 300 mm, and prebaked (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

光 Photoacid generator shown below: 8 parts by mass

ク エ ン Quencher shown below: 5 parts by mass (the mass ratio was 0.1: 0.3: 0.3: 0.2 in order from the left). In addition, among the following quenchers, the polymer type quencher has a weight average molecular weight (Mw) of 5000. 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) Among the following hydrophobic resins, the hydrophobic resin on the left side has a weight average molecular weight. (Mw) is 7000, and the weight average molecular weight (Mw) of the right hydrophobic resin is 8000. 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). Then, it heated at 120 degreeC for 60 second. Subsequently, each developing solution (chemical solution) was developed by paddle for 30 seconds. Next, the wafer was rotated at 4000 rpm for 30 seconds to form a negative resist pattern. Then, 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) having a line / space ratio of 1: 1 was obtained.
In the space portion of the obtained sample, the presence or absence of the above-described metal residue defect, composite residue defect, and spot-like residue defect was evaluated according to the above method.

In each example, the difference in pressure between the filters was 0.01 to 0.03 MPa.
In Table 1, "Usage 1" in the "Usage" column means that the above test was carried out using the chemical solutions described in each of Examples and Comparative Examples as a pre-wet liquid and a rinsing liquid. “Use 2” in the “use” column means that the above test was performed using the chemicals described in each of the examples and comparative examples as a developer.
In the table, “metal residue on Si” indicates the evaluation result of metal residue defect on the silicon substrate, and “composite residue on Si” indicates the result of composite residue defect on the silicon substrate. shows the evaluation results, the "stain-like residue on Si", shows the evaluation results of the stain-like residue defects on the silicon substrate, the "metal residue on SiO _2", a silicon oxide film-silicon substrate Shows the evaluation results of the metal residue defect, and “Composite residue on SiO ₂ ” shows the evaluation result of the composite residue defect on the silicon substrate provided with the silicon oxide film.

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

In Table 1, the data relating to each of the examples and the comparative examples are shown in 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], which are shown in each row of <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”. As shown in Table 1 [Part 1] <3>, the oxidized Ti particles / Ti ion in the chemical solution is 3.5E + 04, and as shown in Table 1 [Part 1] <4>, the Al ion The amount was 32 mass ppt, and as shown in Table 1 [Part 1] <5>, the ratio of 0.5-17 nm Fe oxide particles was 81% by 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 medicinal solution of the present invention could provide a predetermined effect.
In particular, comparison of Examples 1 to 8 confirmed that the effect was more excellent when the mass ratio of the content of titanium oxide particles to the content of titanium ions was 10 ¹ to 10 ¹⁰ .
Further, from Examples 9 and 10, it was confirmed that the effect was more excellent when the mass ratio of the content of iron oxide particles to the content of iron ions was 10 ⁰ to 10 ¹² .
Also, from Examples 11 and 12, to the content of aluminum ions, when the mass ratio of the content of aluminum oxide particles is 10 0 ^to 10 ^12, it was confirmed that more effective is excellent.
Further, according to Examples 13 and 14 (34 and 35, 55 and 56, 76 and 77), the content of titanium ion (or iron ion or aluminum ion) was 0.10 to 100 with respect to the total mass of the chemical solution. It was confirmed that the effect was more excellent when the mass was ppt.
Further, according to Examples 16 and 17 (37 and 38, 58 and 59, 79 and 80), the content of the titanium oxide particles (or the iron oxide particles and the aluminum oxide particles) was reduced by the content of the titanium component in the metal component. On the other hand, when the content was 5% by mass or more and less than 99% by mass, it was confirmed that the effect was more excellent.
Further, according to Examples 18 and 19 (39 and 40, 60 and 61, 81 and 82), of titanium oxide particles (or iron oxide particles and aluminum oxide particles), particles having a particle size of 0.5 to 17 nm were obtained. When the proportion was 60% by mass or more and less than 98% by mass, it was confirmed that the effect was more excellent.
Further, according to 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 cleaning the container (EP-SUS) and various devices used in the <purification procedure> using the chemical solution of Example 22 (100 L), the separately prepared chemical solution of Example 22 was passed through the washed device, The solution was collected in a washed container, and a solution A was obtained in the container.
After cleaning the container (EP-SUS) and various devices used in <Purification Procedure> using the chemical solution (100 L) of Example 38, the chemical solution of Example 22 separately prepared was poured into the above-described washed device. Then, the solution was collected in a washed container, and a solution B was obtained in the container.
When the “metal residue defect on Si” was evaluated using the solution A and the solution B, better results were obtained with the 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 (commercially available, high purity grade): 67.5 g
・ Ethyl lactate (commercially available, high purity grade): 75 g

・ Resin (A-1)
The following resin was used as the resin (A-1).

.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, the resist composition 1 was applied on a silicon wafer having a diameter of 300 mm, and baked (PB: Prebake) at 100 ° C. for 60 seconds to form a resist film having a thickness of 30 nm.

The 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). Thereafter, heating (PEB: Post Exposure Bake) was performed at 85 ° C. for 60 seconds. Next, a developing solution (butyl acetate / manufactured by FETW) was sprayed for 30 seconds by a spray method for development, and a rinsing liquid was discharged onto a silicon wafer for 20 seconds by a spin coating method to be rinsed. Subsequently, the silicon wafer was rotated at a rotation speed of 2000 rpm for 40 seconds to form a line-and-space pattern having a space width of 20 nm and a pattern line width of 15 nm.
As the rinsing liquid, the chemical liquid used in Example 44 described above was used. When the above-described various evaluations were performed, desired effects having the same tendency as in Table 1 were obtained.

Claims (19)

1. A chemical solution containing an organic solvent and a metal component,
   The metal component contains titanium oxide particles, and titanium ions,
   The relative content of titanium ions, the mass ratio of the content of the titanium oxide particles is 10 0 ^to 10 ^12, the drug solution.
2. 薬 The chemical solution according to claim 1, wherein the content of the titanium ion is 0.10 to 100 mass ppt with respect to the total mass of the chemical solution.
3. The chemical solution according to claim 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 claims 1 to 3, wherein the ratio of the particles having a particle size of 0.5 to 17 nm in the titanium oxide particles is 60% by mass or more and less than 98% by mass.
5. The metal component contains iron ions,
   The drug solution according to any one of claims 1 to 4, wherein the content of the iron ions is 0.10 to 100 mass ppt based on the total mass of the drug solution.
6. 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 based on the content of the iron component in the metal component.
7. The metal component contains iron oxide particles,
   The drug solution according to any one of claims 1 to 6, wherein a ratio of particles having a particle size of 0.5 to 17 nm in the iron oxide particles is 60% by mass or more and less than 98% by mass.
8. The metal component contains iron oxide particles, and iron ions,
   The relative content of iron ions, the mass ratio of the content of the iron oxide particles is 10 0 ^to 10 ^12, the drug solution according to any one of claims 1 to 7.
9. The metal component contains an aluminum ion,
   9. The chemical solution according to claim 1, wherein the content of the aluminum ion 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,
    10. The chemical solution according to claim 1, wherein the content of the aluminum oxide particles is 5% by mass or more and less than 99% by mass based on 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 claims 1 to 10, wherein a proportion of the 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 relative amount of aluminum ions, the mass ratio of the content of aluminum oxide particles is 10 0 ^to 10 ^12, the drug solution according to any one of claims 1 to 11.
13. The metal component contains copper oxide particles,
    13. The chemical solution according to claim 1, wherein the content of the copper oxide particles is 5% by mass or more and less than 99% by mass based on the content of the copper component in the metal component.
14. The metal component contains copper oxide particles,
    14. The chemical solution according to claim 1, wherein a proportion of the 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 relative amount of copper ions, the mass ratio of the content of copper oxide particles is 10 0 ^to 10 ^12, the drug solution according to any one of claims 1 to 14.
16. In addition, it contains organic impurities,
    The chemical solution according to any one of claims 1 to 15, wherein the content of the organic impurities is 1,000 to 100,000 mass ppt based on the total mass of the chemical solution.
17. The chemical according to any one of claims 1 to 16, wherein the content of water with respect to the total mass of the chemical 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 -From heptanone, butyl butyrate, isobutyl isobutyrate, isoamyl ether and undecane That contains at least one element selected from the group drug solution according to any one of claims 1 to 17.
19. 薬 A drug solution container comprising a container and the drug solution according to any one of claims 1 to 18 stored in the container.