WO2020040034A1

WO2020040034A1 - Chemical solution accommodation body

Info

Publication number: WO2020040034A1
Application number: PCT/JP2019/032036
Authority: WO
Inventors: 清水　哲也; 上村　哲也; 大松　禎; 智美高橋
Original assignee: 富士フイルム株式会社
Priority date: 2018-08-20
Filing date: 2019-08-15
Publication date: 2020-02-27
Also published as: KR20210032486A; JPWO2020040034A1; TW202026764A

Abstract

The present invention addresses the problem of providing a chemical solution accommodation body which accommodates a chemical solution having excellent defect suppression performance. This chemical solution accommodation body has: a container; and a chemical solution accommodated in the container. The chemical solution contains: a solvent; metal-containing particles including metal atoms; and an organic compound having a ClogP value higher than that of the solvent, wherein the content of the metal-containing particles is 10 mass-ppt or less with respect to the total mass of the chemical solution, a gas, which contains the organic compound having the ClogP value higher than that of the solvent, is present in the vacant space of the container, and the total content of the organic compound in the gas and the organic compound in the chemical solution is 100,000 mass-ppt or less with respect to the total mass of the chemical solution.

Description

Chemical container

The present invention relates to a drug solution container.

In manufacturing a semiconductor device by a wiring forming process including photolithography, a pre-wet solution, a resist solution, a developing solution, a rinsing solution, a stripping solution, a chemical mechanical polishing (CMP) slurry, and a cleaning solution after CMP For example, a chemical solution containing water and / or an organic solvent is used.

The chemical solution is stored in a container after manufacture, and after being stored in a form of a chemical solution container for a certain period of time, the stored chemical solution is taken out and used.
As such a chemical container, Patent Document 1 discloses “a glass container in which the inner surface is treated with a fluorocarbon gas and a sulfurous acid gas while heating, and containing a novolak resin-based positive photoresist solution using an organic solvent. And a novolak resin-based positive photoresist glass container.

JP-A-11-29148

Various impurities contained in the chemical solution may cause defects of the semiconductor device. Such a defect may cause a reduction in the manufacturing yield of the semiconductor device and an electrical abnormality such as a short circuit.
The present inventors have taken out a chemical solution from a chemical solution container and applied it to a wiring forming process including photolithography. As a result, it has been found that a defect may occur in a wiring substrate.

Therefore, an object of the present invention is to provide a chemical solution container that stores a chemical solution having excellent defect suppression performance.

The present inventors have conducted intensive studies on the above problems, and as a result, in a chemical solution container in which the content of metal-containing particles is within a predetermined range, the content of the organic compound in the chemical solution and the presence of It has been found that a chemical solution having excellent defect suppression performance can be obtained if the total of the content of the organic compound and the content of the organic compound is within a predetermined range with respect to the total mass of the chemical solution.
That is, the present inventors have found that the above problem can be solved by the following constitution.

[1]
A container, and a liquid medicine contained in the container, a liquid medicine container,
The chemical solution contains a solvent, metal-containing particles containing a metal atom, and an organic compound having a higher ClogP value than the solvent,
The content of the metal-containing particles is 10 mass ppt or less with respect to the total mass of the chemical solution,
A gas containing an organic compound having a higher ClogP value than the solvent is present in the cavity of the container, and the total content of the organic compound in the gas and the organic compound in the chemical solution is the total mass of the chemical solution. Liquid medicine container having a mass of 100,000 mass ppt or less.
[2]
The content of the metal-containing particles is 0.001 to 10 mass ppt, based on the total mass of the chemical solution;
The chemical solution according to [1], wherein the total content of the organic compound in the gas and the organic compound in the chemical solution is 0.1 to 100,000 mass ppt based on the total mass of the chemical solution. Container.
[3]
[1] or [2], wherein the total mass ratio of the content of the organic compound in the gas and the content of the organic compound in the chemical solution to the content of the metal-containing particles is 0.01 to 100,000. ] The chemical | medical solution container of Claim.
[4]
The drug solution container according to any one of [1] to [3], wherein each of the organic compound in the gas and the organic compound in the drug solution has a ClogP value of 6 or more.
[5]
The drug solution container according to any one of [1] to [4], wherein the organic compound in the gas and the organic compound in the drug solution both contain a phthalate ester.
[6]
The drug solution container according to [5], wherein the phthalate ester includes at least one selected from the group consisting of dioctyl phthalate and diisononyl phthalate.
[7]
The drug solution container according to [6], wherein the mass ratio of the dioctyl phthalate content to the diisononyl phthalate content is 1 or more.
[8]
The drug solution container according to any one of [1] to [7], wherein the mass ratio of the content of the organic compound in the drug solution to the content of the organic compound in the gas is 1 or more.
[9]
The drug solution container according to any one of [1] to [8], wherein the solvent is an organic solvent.
[10]
The organic solvent is cyclohexanone, butyl acetate, N-methyl-2-pyrrolidone, 4-methyl-2-pentanol, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene carbonate, isoamyl acetate, propylene glycol Monomethyl ether, propylene glycol monopropyl ether, methyl methoxypropionate, cyclopentanone, γ-butyrolactone, diisoamyl ether, isopropanol, dimethyl sulfoxide, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, sulfolane, cyclohepta Non and 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate Isopentyl propionate, ethyl cyclohexane, is at least one selected from the group consisting of mesitylene, and decane, chemical container according to [9].
[11]
Among the metal-containing particles, the number of metal nanoparticles having a particle size of 0.5 to 17 nm per unit volume of the chemical solution is 1.0 × 10 ¹ to 1.0 × 10 ⁹ / cm ³ . A drug solution container according to any one of [1] to [10].
[12]
The gas contains nitrogen gas,
The content of the nitrogen gas is 95 to 99.9999% by volume based on the total volume of the voids,
The drug solution container according to any one of [1] to [11], wherein the content of the organic compound in the gas is 0.05 to 50,000 mass ppt with respect to the total mass of the drug solution.
[13]
The drug solution container according to any one of [1] to [12], wherein the porosity of the container in the drug solution container is 50 to 99.99% by volume.
[14]
The chemical liquid container according to any one of [1] to [13], wherein at least a part of the liquid contact part of the container is a fluororesin, electropolished stainless steel, or glass.
[15]
When at least a part of the liquid contact part of the container is the electropolished stainless steel,
The liquid medicine container according to [14], wherein the liquid contact part of the container has an average surface roughness Ra of less than 100 nm.
[16]
The drug solution container according to [14], wherein at least a part of the liquid contact part of the container further includes a conductive material together with the fluororesin.
[17]
The drug solution container according to [16], wherein the conductive material contains carbon.
[18]
The chemical solution container according to [17], wherein the carbon is at least one selected from the group consisting of carbon particles, carbon nanotubes, and carbon fillers.
[19]
At least one selected from the group consisting of a developer, a rinse, a wafer cleaning liquid, a line cleaning liquid, a pre-wet liquid, a resist liquid, a lower layer film forming liquid, an upper layer film forming liquid, and a hard coat forming liquid; The liquid medicine container according to any one of [1] to [18], which is used as a raw material of the liquid.

According to the present invention, as described below, it is possible to provide a chemical solution container that stores a chemical solution having excellent defect suppression performance.

Hereinafter, the present invention will be described.
The description of the constituent requirements 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 )”.
In addition, in the notation of the group (atom group) in the present invention, the notation that does not denote substituted or unsubstituted includes those not having a substituent and those having a substituent as long as the effects of the present invention are not impaired. Includes 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 synonymous with each compound.
Further, the “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.

[Chemical container]
The drug solution container of the present invention (hereinafter, also referred to as “the drug solution container”) is a drug solution container having a container and a drug solution contained in the container.
In the present chemical solution container, the chemical solution includes a solvent, metal-containing particles containing metal atoms, and an organic compound having a higher ClogP value than the solvent (hereinafter, also referred to as “specific organic compound A”). contains.
Further, in the present chemical solution container, the content of the metal-containing particles is 10 mass ppt or less with respect to the total mass of the chemical solution.
Further, in the medicinal liquid container, a gas containing an organic compound having a higher ClogP value than the solvent (hereinafter, also referred to as “specific organic compound B”) exists in the space of the container, and the specific organic compound A and the gas are present. The total content of the specific organic compound B is 100,000 mass ppt or less based on the total mass of the chemical solution.
The mechanism by which the above-mentioned problem is solved by the present medicinal solution container is not necessarily clear, but the present inventors speculate on 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 organic compound and the metal-containing particles contained in the chemical solution themselves cause defects, but they are liable to aggregate to form composite particles that cause defects. In particular, when an organic compound (specific organic compound) having a ClogP value higher than that of the solution is included, composite particles of the specific organic compound and the metal-containing particles are easily formed, and the generation of defects becomes remarkable.
As a solution to this problem, a method of reducing the content of the specific organic compound in the chemical solution can be considered. However, this method may not be able to sufficiently suppress the occurrence of defects.
It is considered that the reason for this is that the specific organic compound contained in the gas in the cavity of the container is mixed into the chemical solution when the chemical solution container is transported and stored. In other words, when the chemical is stored in the container, the content of the specific organic compound becomes larger than immediately after the production of the chemical (before storing in the container), and the occurrence of defects may be significant.
Since the total content of the specific organic compound A and the specific organic compound B is within the above range in the present chemical solution container, it is presumed that a chemical solution container containing a chemical solution with excellent defect suppression performance was obtained.

(Chemical solution)
The chemical solution contains a solvent, metal-containing particles containing metal atoms, and an organic compound (specific organic compound A) having a higher ClogP value than the solvent.

<Solvent>
The chemical solution contains a solvent. Examples of the solvent include at least one of water and an organic solvent, and an organic solvent is preferable.
In addition, in this specification, the organic solvent is intended to be a liquid organic compound contained at a content exceeding 10,000 ppm by mass per component with respect to the total mass of the drug 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 drug solution corresponds to an organic solvent.
In this specification, the term “liquid” means a liquid at 25 ° C. and atmospheric pressure.

The type of the organic solvent is not particularly limited, and a known organic solvent is 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 optionally having a ring Examples include compounds (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.
As the organic solvent, for example, those described in JP-A-2016-57614, JP-A-2014-219664, JP-A-2016-138219, and JP-A-2015-135379 may be used. Good.

As the organic solvent, propylene glycol monomethyl ether, propylene glycol monoethyl ether (PGME), propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), methyl methoxypropionate, cyclopentanone, cyclohexanone (CHN), γ-butyrolactone, diisoamyl ether, butyl acetate (nBA), isoamyl acetate (iAA), isopropanol, 4-methyl-2-pentanol (MIBC), dimethyl sulfoxide, N-methyl-2-pyrrolidone (NMP ), Diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, propylene carbonate (PC), sulfolane, cyclohexane Thanong, 1-hexanol, decane, 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, isopentyl propionate, ethyl cyclohexane, and, at least one selected from the group consisting of mesitylene preferred.
Among them, CHN, nBA, NMP, EL, PGMEA, PGME, PC, iAA, propylene glycol monomethyl ether, propylene glycol monopropyl ether, methyl methoxypropionate, cyclopentanone, γ- Butyrolactone, diisoamyl ether, isopropanol, dimethyl sulfoxide, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, sulfolane, cycloheptanone, 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, propionate At least one selected from the group consisting of isopentyl acid, ethylcyclohexane, mesitylene and decane is more preferred.

The content of the organic solvent in the chemical solution is not particularly limited, but is generally preferably 98.0% by mass or more, more preferably 99.0% by mass or more, and preferably 99.9% by mass or more based on the total mass of the chemical solution. More preferably, it is particularly preferably at least 99.99 mass%. The upper limit is not particularly limited, but is often less than 100% by mass.
One organic solvent may be used alone, or two or more organic solvents may be used in combination. When two or more organic solvents are used in combination, the total content is preferably within the above range.
In addition, the kind and content of the organic solvent in the chemical solution can be measured using a gas chromatograph mass spectrometer.

<Metal-containing particles>
The chemical solution contains metal-containing particles containing metal atoms.
A preferred embodiment of the method for producing a chemical solution will be described later. Generally, the chemical solution can be produced by purifying a substance to be purified containing the solvent and the organic compound described above. The metal-containing particles may be intentionally added in the manufacturing process of the chemical solution, may be originally contained in the object to be purified, or may be transferred from the manufacturing device of the chemical solution in the manufacturing process of the chemical solution (so-called (Contamination).

The metal atom is not particularly limited, and examples thereof include an Fe atom, an Al atom, a Cr atom, a Ni atom, a Pb atom, a Zn atom, and a Ti atom. Above all, when the content of metal-containing particles containing Fe atom, Al atom, Pb atom, Zn atom, and Ti atom in a chemical solution is strictly controlled, more excellent defect suppression performance is easily obtained, and Pb atom If the content of the metal-containing particles containing Ti atoms in the chemical solution is strictly controlled, more excellent defect suppression performance can be easily obtained.
That is, the metal atom is preferably at least one selected from the group consisting of Fe atom, Al atom, Cr atom, Ni atom, Pb atom, Zn atom, Ti atom, and the like. Fe atom, Al atom, Pb At least one selected from the group consisting of atoms, Zn atoms, and Ti atoms is more preferable, and at least one selected from the group consisting of Pb atoms and Ti atoms is still more preferable. It is particularly preferable to contain both atoms and Ti atoms.
The metal-containing particles may contain one kind of the above-mentioned metal atoms alone or may contain two or more kinds thereof in combination.

The particle size of the metal-containing particles is not particularly limited. For example, in a chemical solution for manufacturing a semiconductor device, the content of particles having a particle size of about 0.1 to 100 nm in the chemical solution may be controlled. Many.
In particular, according to the study of the present inventors, in a chemical solution applied to a photoresist process of EUV (extreme ultraviolet) exposure, metal-containing particles having a particle diameter of 0.5 to 17 nm (hereinafter, referred to as “metal”) It has been found that by controlling the content of “nanoparticles” in a chemical solution, a chemical solution having excellent defect suppression performance can be easily obtained. In a photoresist process of EUV exposure, a fine resist interval, a resist width, and a resist pitch are often required. In such a case, it is required to control finer particles in units of the number, which has not been a problem in the conventional process.

The number-based particle size distribution of the metal-containing particles is not particularly limited, but is comprised of a range of less than 5 nm, and a range of more than 17 nm, in that a drug solution having better effects of the present invention can be obtained. It is preferable that at least one selected from the group has a maximum value.
In other words, it is preferable that the particle diameter has no maximum value in the range of 5 to 17 nm. By not having a maximum value in the range of the particle diameter of 5 to 17 nm, the chemical solution has more excellent defect suppression performance, particularly more excellent bridge defect suppression performance. Here, the bridge defect means a defect like a bridge between wiring patterns.
In addition, it is particularly preferable that the particle diameter has a maximum value in a range of 0.5 nm or more and less than 5 nm in a number-based particle diameter distribution, from the viewpoint that a drug solution having a more excellent effect of the present invention can be obtained. As described above, the chemical solution has more excellent bridge defect suppression performance.

The content of the metal-containing particles is 10 mass ppt or less, preferably 0.001 to 10 mass ppt, based on the total mass of the chemical solution.
When the content of the metal-containing particles is 10 mass ppt or less, defects due to aggregates of the metal-containing particles can be suppressed. If the content of the metal-containing particles is 0.01 mass ppt or more, the detailed reason is unknown, but the interaction between the metal-containing particles and the wiring board becomes small, and the metal-containing particles hardly remain on the substrate. And defects can be suppressed.
The upper limit of the content of the metal-containing particles is preferably 5 mass ppt or less, more preferably 1 mass ppt or less, and particularly preferably 0.1 mass ppt or less, from the viewpoint that the above-mentioned effects are more exhibited.
The lower limit of the content of the metal-containing particles is preferably 0.001 mass ppt or more, and particularly preferably 0.01 mass ppt or more, from the viewpoint that the above effects are more exhibited.

The type and content of metal-containing particles in a chemical solution can be measured by the 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. The metal component means metal ions and metal-containing particles. 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, 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 component in the sample.
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.

(Metal nanoparticles)
Metal nanoparticles refer to metal-containing particles having a particle diameter of 0.5 to 17 nm.
The number of metal nanoparticles contained per unit volume of the chemical solution is preferably 1.0 × 10 ⁰ to 1.0 × 10 ⁹ particles / cm ³ , and the content of the metal nanoparticles is more excellent in that the chemical solution has the effect of the present invention. The number is preferably 1.0 × 10 ¹ / cm ³ or more, more preferably 1.0 × 10 ⁷ / cm ³ or less, and even more preferably 1.0 × 10 ⁵ / cm ³ or less.
When the number of particles of metal nanoparticles per unit volume of the chemical solution is 1.0 × 10 ¹ to 1.0 × 10 ⁹ / cm ³ , the chemical solution has more excellent defect suppression performance.
The content of the metal nanoparticles in the drug solution can be measured by the method described in Examples, and the number (number) of metal nanoparticles per unit volume of the drug solution is rounded to two significant figures. Ask for it.

金属 The metal atoms contained in the metal nanoparticles are not particularly limited, but are the same as the atoms already described as the metal atoms contained in the metal-containing particles. Among them, at least one selected from the group consisting of Pb atoms and Ti atoms is preferable as the metal atom in that a chemical solution having more excellent effects of the present invention can be obtained, and the metal nanoparticles are preferably Pb atoms. , And more preferably contain both Ti atoms. The phrase that the metal nanoparticles contain both Pb atoms and Ti atoms typically includes a form in which the chemical solution contains both metal nanoparticles containing Pb atoms and metal nanoparticles containing Ti atoms. .

In addition, metal nanoparticles containing Pb atoms (hereinafter also referred to as “Pb nanoparticles”) and metal nanoparticles containing Ti atoms (hereinafter also referred to as “Ti nanoparticles”) in a chemical solution. Although the number ratio (Pb / Ti) is not particularly limited, it is generally preferably 1.0 × 10 ⁻⁴ to 3.0, more preferably 1.0 × 10 ⁻³ to 2.0, and more preferably 1.0 × 10 ⁻³ to 2.0. Particularly preferred is ^-2 to 1.5. When Pb / Ti is from 1.0 × 10 ⁻³ to 2.0, the chemical solution has more excellent effects of the present invention, particularly, more excellent bridging defect suppression performance.
According to the present invention, Pb nanoparticles and Ti nanoparticles are likely to associate with each other, for example, when a chemical solution is applied on a wafer, and easily cause defects (especially, bridge defects) when developing a resist film. They know.
Surprisingly, when Pb / Ti is 1.0 × 10 ⁻³ to 2.0, the occurrence of defects is more likely to be suppressed. In this specification, Pb / Ti and A / (B + C) described later are obtained by rounding off to two significant figures.

The metal nanoparticles only need to contain metal atoms, and the form is not particularly limited. For example, a simple substance of a metal atom, a compound containing a metal atom (hereinafter, also referred to as a “metal compound”), a complex thereof, and the like can be given. Further, the metal nanoparticles may contain a plurality of metal atoms. When the metal nanoparticles contain a plurality of metals, a metal atom having the largest content (atm%) of the plurality of metals is used as a main component. Therefore, when the term “Pb nanoparticle” includes a plurality of metals, it means that the Pb atom is a main component among the plurality of metals.

The complex is not particularly limited, but is a so-called core-shell type particle having a simple substance of a metal atom and a metal compound covering at least a part of the simple substance of the metal atom, and a solid solution including the metal atom and another atom. Particles, eutectic particles containing metal atoms and other atoms, aggregate particles of a single metal atom and a metal compound, aggregate particles of different types of metal compounds, and continuous or Examples thereof include metal compounds whose composition changes intermittently.

原子 The atom other than the metal atom contained in the metal compound is not particularly limited, but examples thereof include a carbon atom, an oxygen atom, a nitrogen atom, a hydrogen atom, a sulfur atom, and a phosphorus atom, and among them, an oxygen atom is preferable. The form in which the metal compound contains an oxygen atom is not particularly limited, but an oxide of a metal atom is more preferable.

From the viewpoint that a chemical solution having a better effect of the present invention can be obtained, as metal nanoparticles, particles composed of a single metal atom (particle A), particles composed of an oxide of a metal atom (particle B), and metal It is preferably made of at least one selected from the group consisting of particles consisting of elemental atoms and oxides of metal atoms (particles C).
The relationship between the number of particles A, the number of particles B, and the number of particles C in the number of particles of metal nanoparticles per unit volume of the drug solution is not particularly limited. The ratio of the number of particles contained in particles A to the total number of particles contained in particles B and particles C (hereinafter, “A / (B + C) ”) is preferably 1.5 or less, more preferably less than 1.0, further preferably 2.0 × 10 ⁻¹ or less, particularly preferably 1.0 × 10 ⁻¹ or less. 0.0 × 10 ⁻³ or more is preferable, and 1.0 × 10 ⁻² or more is more preferable.
When A / (B + C) is less than 1.0, the chemical solution has better bridging defect suppression performance, better pattern width uniformity performance, and spot-like defect suppression performance. In addition, the spot-like defect means a defect in which no metal atom is detected.
When A / (B + C) is 0.1 or less, the chemical has more excellent defect suppression performance.

<Specific organic compound A>
The chemical solution contains the specific organic compound A. As described above, the specific organic compound A is an organic compound having a higher ClogP value than the solvent in the chemical solution.
The specific organic compound A may be added to the chemical solution, or may be unintentionally mixed in the manufacturing process of the chemical solution. Examples of the case where they are unintentionally mixed in the manufacturing process of the chemical solution include, for example, the case where the specific organic compound A is contained in a raw material (eg, an organic solvent) used for manufacturing the chemical solution, and the case where the specific organic compound A is mixed in the manufacturing process of the chemical solution. (For example, contamination) and the like, but are not limited thereto.

The specific organic compound A has a higher ClogP value than the solvent in the chemical solution. From the viewpoint that the effect of the present invention is more exerted, the difference between the ClogP value of the specific organic compound A and the ClogP value of the solvent in the chemical solution [(ClogP value of specific organic compound A) − (ClogP value of solvent in the chemical solution)] Is preferably 3 to 9, preferably 3 to 8, and more preferably 4 to 7.
The ClogP value of the specific organic compound A is not particularly limited as long as it is higher than the solvent in the drug solution, but is preferably 6 or more, particularly preferably 6 to 10, from the viewpoint that the effect of the present invention is more exhibited.
Here, the ClogP value is a value obtained by calculating a common logarithm logP of a partition coefficient P to 1-octanol and water. Known methods and software can be used for calculating the ClogP value. However, unless otherwise specified, the present invention uses the ClogP program incorporated in ChemBioDrawUltra 12.0 of Cambridgesoft.
For example, the ClogP value of dibutyl phthalate is 4.72, the ClogP value of dioctyl phthalate (DOP) is 8.71, and the ClogP value of diisononyl phthalate (DINP) is 9.03.

炭素 The carbon number of the specific organic compound A is not particularly limited, but is preferably 8 or more, more preferably 12 or more, from the viewpoint that the chemical solution has more excellent effects of the present invention. The upper limit of the number of carbon atoms is not particularly limited, but is preferably 30 or less.

The specific organic compound A may be, for example, a by-product generated during the synthesis of the organic solvent and / or an unreacted raw material (hereinafter, also referred to as “by-product or the like”).
Examples of the by-products and the like include compounds represented by the following formulas IV.

In Formula I, R ₁ and R ₂ each independently represent an alkyl group or a cycloalkyl group, or combine with each other to form a ring.

The alkyl group or cycloalkyl group represented by R ₁ and R ₂ is preferably an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 6 to 12 carbon atoms, and is preferably an alkyl group having 1 to 8 carbon atoms. A group or a cycloalkyl group having 6 to 8 carbon atoms is more preferred.

The ring formed by combining R ₁ and R ₂ with each other is a lactone ring, preferably a 4- to 9-membered lactone ring, more preferably a 4- to 6-membered lactone ring.

Preferably, R ₁ and R ₂ satisfy the relationship that the compound represented by the formula I has 8 or more carbon atoms.

In Formula II, R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, or a cycloalkenyl group, or combine with each other to form a ring. However, R ₃ and R ₄ are not both hydrogen atoms.

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

The alkenyl group represented by R ₃ and R ₄ is, for example, preferably an alkenyl group having 2 to 12 carbon atoms, and more preferably an alkenyl group having 2 to 8 carbon atoms.

The cycloalkyl group represented by R ₃ and R ₄ is preferably a cycloalkyl group having 6 to 12 carbon atoms, and more preferably a cycloalkyl group having 6 to 8 carbon atoms.

As the cycloalkenyl group represented by R ₃ and R ₄ , for example, a cycloalkenyl group having 3 to 12 carbon atoms is preferable, and a cycloalkenyl group having 6 to 8 carbon atoms is more preferable.

The ring formed by R ₃ and R ₄ bonded to each other has a cyclic ketone structure, and may be a saturated cyclic ketone or an unsaturated cyclic ketone. This cyclic ketone preferably has a 6- to 10-membered ring, more preferably a 6- to 8-membered ring.

Preferably, R ₃ and R ₄ satisfy the relationship that the compound represented by Formula II has 8 or more carbon atoms.

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

The alkyl group represented by R ₅ is preferably an alkyl group having 6 or more carbon atoms, more preferably an alkyl group having 6 to 12 carbon atoms, and particularly preferably an alkyl group having 6 to 10 carbon atoms.
The alkyl group may have an ether bond in the chain, or may have a substituent such as a hydroxy group.

The cycloalkyl group represented by R ₅ is preferably a cycloalkyl group having 6 or more carbon atoms, more preferably a cycloalkyl group having 6 to 12 carbon atoms, and particularly preferably a cycloalkyl group having 6 to 10 carbon atoms.

In Formula IV, R ₆ and R ₇ each independently represent an alkyl group or a cycloalkyl group, or combine with each other to form a ring.

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

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

The ring formed by combining R ₆ and R ₇ with each other has a cyclic ether structure. This cyclic ether structure is preferably a 4- to 8-membered ring, more preferably a 5- to 7-membered ring.

Preferably, R ₆ and R ₇ satisfy the relationship that the compound represented by the formula IV has 8 or more carbon atoms.

In Formula V, R ₈ and R ₉ each independently represent an alkyl group or a cycloalkyl group, or combine with each other to form a ring. L represents a single bond or an alkylene group.

As the alkyl group represented by R ₈ and R ₉ , for example, an alkyl group having 6 to 12 carbon atoms is preferable, and an alkyl group having 6 to 10 carbon atoms is more preferable.

The cycloalkyl group represented by R ₈ and R ₉ is preferably a cycloalkyl group having 6 to 12 carbon atoms, and more preferably a cycloalkyl group having 6 to 10 carbon atoms.

The ring formed by combining R ₈ and R ₉ with each other has a cyclic diketone structure. This cyclic diketone structure is preferably a 6- to 12-membered ring, more preferably a 6- to 10-membered ring.

As the alkylene group represented by L, for example, an alkylene group having 1 to 12 carbon atoms is preferable, and an alkylene group having 1 to 10 carbon atoms is more preferable.
Note that R ₈ , R ₉ and L satisfy the relationship that the compound represented by the formula V has 8 or more carbon atoms.
Although not particularly limited, when the organic solvent is an amide compound, an imide compound, and a sulfoxide compound, in one embodiment, an amide compound, an imide compound, and a sulfoxide compound having 6 or more carbon atoms are used. In addition, examples of the specific organic compound A include the following compounds.

Specific organic compounds A include dibutylhydroxytoluene (BHT), distearylthiodipropionate (DSTP), 4,4′-butylidenebis- (6-t-butyl-3-methylphenol), 2,2 ′ -Methylene bis- (4-ethyl-6-t-butylphenol) and antioxidants such as antioxidants described in JP-A-2005-200775; unreacted raw materials; structures generated during production of organic solvents Isomers and by-products; eluates from members and the like constituting an organic solvent production device (for example, a plasticizer eluted from a rubber member such as an O-ring); and the like.

Examples of the specific organic compound A include dioctyl phthalate (DOP), bis (2-ethylhexyl) phthalate (DEHP), bis (2-propylheptyl) phthalate (DPHP), dibutyl phthalate (DBP), and phthalic acid. Phthalic acid esters such as benzyl butyl (BBzP), diisodecyl phthalate (DIDP), diisooctyl phthalate (DIOP), diethyl phthalate (DEP), diisobutyl phthalate (DIBP), dihexyl phthalate and diisononyl phthalate (DINP); Tris (2-ethylhexyl) trimellitate (TEHTM), Tris (n-octyl-n-decyl) trimellitate (ATM), Bis (2-ethylhexyl) adipate (DEHA), Monomethyl adipate (MMAD), Adipine Dioctyl acid (DOA), Dibutyl bacinate (DBS), dibutyl maleate (DBM), diisobutyl maleate (DIBM), azelaic acid ester, benzoic acid ester, terephthalate (eg, dioctyl terephthalate (DEHT)), diisononyl 1,2-cyclohexanedicarboxylate ( DINCH), epoxidized vegetable oil, sulfonamides (eg, N- (2-hydroxypropyl) benzenesulfonamide (HP BSA), N- (n-butyl) benzenesulfonamide (BBSA-NBBS)), organic phosphates ( Examples: tricresyl phosphate (TCP), tributyl phosphate (TBP)), acetylated monoglyceride, triethyl citrate (TEC), acetyl triethyl citrate (ATEC), tributyl citrate (TBC), acetyl citrate Butyl (ATBC), trioctyl citrate (TOC), acetyl trioctyl citrate (ATOC), trihexyl citrate (THC), acetyl trihexyl citrate (ATHC) epoxidized soybean oil, ethylene propylene rubber, polybutene, -Ethylidene-2-norbornene addition polymers, and the following polymeric plasticizers are also exemplified.
It is presumed that these specific organic compounds A are mixed into a substance to be purified or a chemical solution from a filter, a pipe, a tank, an O-ring, a container, or the like that is touched in the purification step. In particular, compounds other than alkyl olefins are associated with the occurrence of bridge defects.

Among the above compounds, the specific organic compound A is generally present in a chemical solution production environment, and is preferably a phthalate ester because its content can be easily adjusted by a production process and a production method, and dioctyl phthalate ( At least one selected from the group consisting of DOP) and diisononyl phthalate (DINP) is preferred.

The content of the specific organic compound A is not particularly limited as long as the total content of the organic compound (organic compound B to be described later) contained in the gas existing in the voids is within the range described below. From the viewpoint of superiority, the amount is preferably 100,000 mass ppt or less, more preferably 0.1 to 1,000 mass ppt, and particularly preferably 0.1 to 10 mass ppt, based on the total mass of the chemical solution.

含有 The content and type of the specific organic compound A in the drug solution can be measured by using GCMS (gas chromatography mass spectrometer; gas chromatography mass spectrometry).

<Other components>
The chemical solution may contain other components other than the above. Examples of the other components include an organic compound other than the specific organic compound A, a resin, and the like.

(Organic compounds other than specific organic compound A)
The chemical solution may contain an organic compound other than the specific organic compound A (hereinafter, also referred to as “other organic compound”). The other organic compound is an organic compound having a ClogP value equal to or less than the ClogP value of the solvent in the chemical solution.
Other organic compounds may be added to the chemical solution or may be mixed unintentionally in the process of manufacturing the chemical solution. Examples of the case where they are unintentionally mixed in the manufacturing process of a chemical solution include, for example, a case where another specific organic compound is contained in a raw material (for example, an organic solvent) used for manufacturing the chemical solution, and a case where the other compound is mixed in the manufacturing process of the chemical solution. (For example, contamination), but is not limited thereto.

(resin)
The chemical solution may contain a resin. As the resin, a resin P having a group that is decomposed by the action of an acid to generate a polar group is more preferable. As the resin, a resin having a repeating unit represented by the following formula (AI), which is a resin whose solubility in a developer containing an organic solvent as a main component is reduced by the action of an acid, is more preferable. The resin having a repeating unit represented by the formula (AI) described below has a group that is decomposed by the action of an acid to generate an alkali-soluble group (hereinafter, also referred to as an “acid-decomposable group”).
Examples of the polar group include an alkali-soluble group. Examples of the alkali-soluble group include a carboxy group, a fluorinated alcohol group (preferably hexafluoroisopropanol group), a phenolic hydroxyl group, and a sulfo group.

The polar group in the acid-decomposable group is protected by an acid-eliminable group (acid-eliminable group). Examples of the acid leaving group include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and —C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ).

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

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

The resin P whose solubility in a developer containing an organic solvent as a main component is reduced by the action of an acid will be described in detail below.

((Formula (AI): a repeating unit having an acid-decomposable group))
The resin P preferably contains a repeating unit represented by the formula (AI).

In the formula (AI),
Xa ₁ represents a hydrogen atom or an alkyl group which may have a substituent.
T represents a single bond or a divalent linking group.
Ra ₁ to Ra ₃ each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic).
Two of Ra ₁ to Ra ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the optionally substituted alkyl group represented by Xa ₁ include a methyl group and a group represented by —CH ₂ —R ₁₁ . R ₁₁ represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group.
Xa ₁ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

Examples of the divalent linking group for T include an alkylene group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, a — (CH ₂ ) ₂ — group, or a — (CH ₂ ) ₃ — group.

The alkyl group of Ra ₁ to Ra ₃ preferably has 1 to 4 carbon atoms.

The cycloalkyl group of Ra ₁ to Ra ₃ may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. Ring cycloalkyl groups are preferred.
Examples of the cycloalkyl group formed by bonding two of Ra ₁ to Ra ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl. Or a polycyclic cycloalkyl group such as an adamantyl group. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.

The cycloalkyl group formed by combining two of Ra ₁ to Ra ₃ is, for example, a group in which one of methylene groups constituting a ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group. It may be replaced.

In the repeating unit represented by the formula (AI), for example, an embodiment in which Ra ₁ is a methyl group or an ethyl group, and Ra ₂ and Ra ₃ are bonded to form the above-described cycloalkyl group is preferable.

Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxy group, And an alkoxycarbonyl group (having 2 to 6 carbon atoms), preferably having 8 or less carbon atoms.

The content of the repeating unit represented by the formula (AI) is preferably from 20 to 90 mol%, more preferably from 25 to 85 mol%, particularly preferably from 30 to 80 mol%, based on all repeating units in the resin P. preferable.

((Repeating unit having lactone structure))
Further, the resin P preferably contains a repeating unit Q having a lactone structure.

The repeating unit Q having a lactone structure preferably has a lactone structure in a side chain, and more preferably a repeating unit derived from a (meth) acrylic acid derivative monomer.
As the repeating unit Q having a lactone structure, one type may be used alone, or two or more types may be used in combination. However, it is preferable to use one type alone.
The content of the repeating unit Q having a lactone structure is preferably from 3 to 80 mol%, more preferably from 3 to 60 mol%, based on all repeating units in the resin P.

As the lactone structure, a 5- to 7-membered lactone structure is preferable, and a structure in which another ring structure is condensed with a 5- to 7-membered lactone structure to form a bicyclo structure or a spiro structure is more preferable.
The lactone structure preferably has a repeating unit having a lactone structure represented by any of the following formulas (LC1-1) to (LC1-17). The lactone structure is preferably a lactone structure represented by the formula (LC1-1), the formula (LC1-4), the formula (LC1-5) or the formula (LC1-8), and is represented by the formula (LC1-4) Lactone structures are more preferred.

The lactone structure part may have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxy group. , A halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may combine with each other to form a ring. .

((Repeating unit having phenolic hydroxyl group))
The resin P may contain a repeating unit having a phenolic hydroxyl group.
Examples of the repeating unit having a phenolic hydroxyl group include a repeating unit represented by the following general formula (I).

Where:
R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₄₂ may combine with Ar ₄ to form a ring, in which case R ₄₂ represents a single bond or an alkylene group.

X ₄ represents a single bond, —COO—, or —CONR ₆₄ —, and R ₆₄ represents a hydrogen atom or an alkyl group.
L ₄ represents a single bond or an alkylene group.
Ar ₄ represents a (n + 1) -valent aromatic ring group, and when it is bonded to R ₄₂ to form a ring, represents an (n + 2) -valent aromatic ring group.
n represents an integer of 1 to 5.

_Examples of the alkyl group of R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and a sec-butyl which may have a substituent. An alkyl group having 20 or less carbon atoms such as a group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group is preferred, an alkyl group having 8 or less carbon atoms is more preferred, and an alkyl group having 3 or less carbon atoms is particularly preferred.

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

Examples of the halogen atom of R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

As the alkyl group contained in the alkoxycarbonyl group of R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I), the same alkyl groups as those described above for R ₄₁ , R ₄₂ and R ₄₃ are preferable.

Examples of the substituent in each of the above groups include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxy group, a carboxy group, a halogen atom, an alkoxy group, a thioether group, and an acyl group. , An acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group, and the substituent preferably has 8 or less carbon atoms.

Ar ₄ represents an (n + 1) -valent aromatic ring group. The divalent aromatic ring group when n is 1 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group and an anthracenylene group; And aromatic ring groups containing a hetero ring such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole and thiazole.

When n is an integer of 2 or more, specific examples of the (n + 1) -valent aromatic ring group include the above-described specific examples of the divalent aromatic ring group obtained by removing (n-1) arbitrary hydrogen atoms. And the group consisting of
The (n + 1) -valent aromatic ring group may further have a substituent.

Examples of the substituent which the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group and (n + 1) -valent aromatic ring group may have include, for example, R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I). The above-mentioned alkyl groups; alkoxy groups such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group; and aryl groups such as phenyl group.

_-CONR 64 represented by X ₄ - _{(R 64} represents a hydrogen atom or an alkyl group) The alkyl group for _{R 64} in, which may have a substituent, a methyl group, an ethyl group, a propyl group, Examples thereof include an alkyl group having 20 or less carbon atoms such as an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and an alkyl group having 8 or less carbon atoms is more preferable.

X ₄ is preferably a single bond, —COO— or —CONH—, more preferably a single bond or —COO—.

As the alkylene group for L _4, an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and an octylene group which may have a substituent is preferable.

Ar ₄ is preferably an optionally substituted aromatic ring group having 6 to 18 carbon atoms, more preferably a benzene ring group, a naphthalene ring group or a biphenylene ring group.

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

The content of the repeating unit having a phenolic hydroxyl group is preferably from 0 to 50 mol%, more preferably from 0 to 45 mol%, particularly preferably from 0 to 40 mol%, based on all repeating units in the resin P.

((A repeating unit containing an organic group having a polar group))
The resin P may further contain a repeating unit containing an organic group having a polar group, in particular, a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. Thereby, the substrate adhesion and the developer affinity are improved.
The alicyclic hydrocarbon structure of the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group, a diamantyl group or a norbornane group. As the polar group, a hydroxyl group or a cyano group is preferable.

When the resin P contains a repeating unit containing an organic group having a polar group, the content is preferably from 1 to 50 mol%, more preferably from 1 to 30 mol%, based on all repeating units in the resin P. More preferably, 5 to 25 mol% is further preferable, and 5 to 20 mol% is particularly preferable.

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

In the general formula (VI),
R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R ₆₂ may be bonded to Ar ₆ to form a ring, in which case R ₆₂ represents a single bond or an alkylene group.
X ₆ represents a single bond, —COO—, or —CONR ₆₄ —. R ₆₄ represents a hydrogen atom or an alkyl group.
L ₆ represents a single bond or an alkylene group.
Ar ₆ represents an (n + 1) -valent aromatic ring group, and when it is bonded to R ₆₂ to form a ring, represents an (n + 2) -valent aromatic ring group.
Y ₂ independently represents a hydrogen atom or a group capable of leaving by the action of an acid when n ≧ 2. However, at least one of Y ₂ represents a group which is eliminated by the action of an acid.
n represents an integer of 1 to 4.

As the group Y _{2 which} is eliminated by the action of an acid, a structure represented by the following general formula (VI-A) is preferable.

L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group obtained by combining an alkylene group and an aryl group.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, a cycloalkyl group optionally containing a hetero atom, an aryl group optionally containing a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group.
At least two members of Q, M and L ₁ may combine to form a ring (preferably a 5- or 6-membered ring).

繰り返し The repeating unit represented by the general formula (VI) is preferably a repeating unit represented by the following general formula (3).

In the general formula (3),
Ar ₃ represents an aromatic ring group.
R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, or a heterocyclic group.
M ₃ represents a single bond or a divalent linking group.
Q ₃ represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.
At least two of Q ₃ , M ₃ and R ₃ may combine to form a ring.

The aromatic ring group represented by Ar ₃ is the same as Ar ₆ in the general formula (VI) when n in the general formula (VI) is 1, a phenylene group or a naphthylene group is preferable, and a phenylene group is more preferable. preferable.

((Repeating unit having silicon atom in side chain))
The resin P may further contain a repeating unit having a silicon atom in a side chain. Examples of the repeating unit having a silicon atom in the side chain include a (meth) acrylate-based repeating unit having a silicon atom and a vinyl-based repeating unit having a silicon atom. The repeating unit having a silicon atom in the side chain is typically a repeating unit having a group having a silicon atom in the side chain. Examples of the group having a silicon atom include a trimethylsilyl group, a triethylsilyl group, and a triphenyl group. Silyl group, tricyclohexylsilyl group, tristrimethylsiloxysilyl group, tristrimethylsilylsilyl group, methylbistrimethylsilylsilyl group, methylbistrimethylsiloxysilyl group, dimethyltrimethylsilylsilyl group, dimethyltrimethylsiloxysilyl group, and the following cyclic Alternatively, a linear polysiloxane, a cage type, a ladder type, or a random type silsesquioxane structure may be used. In the formula, R and R ¹ each independently represent a monovalent substituent. * Represents a bond.

繰り返し As the repeating unit having the above group, for example, a repeating unit derived from an acrylate compound or a methacrylate compound having the above group, or a repeating unit derived from a compound having the above group and a vinyl group is preferable.

When the resin P has a repeating unit having a silicon atom in the side chain, its content is preferably from 1 to 30 mol%, more preferably from 5 to 25 mol%, based on all repeating units in the resin P. Is particularly preferably 5 to 20 mol%.

The weight average molecular weight of the resin P is preferably from 1,000 to 200,000, more preferably from 3,000 to 20,000, more preferably from 5,000 to 15,000 as a polystyrene equivalent value by GPC (Gel Permeation Chromatography). Particularly preferred. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and developability is deteriorated, and viscosity is increased to deteriorate film formability. Can be prevented.

The degree of dispersion (molecular weight distribution) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0.

In the chemical solution, the content of the resin P is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass based on the total solid content.
In the chemical solution, the resin P may be used singly or in combination of two or more.

公知 As other components (for example, an acid generator, a basic compound, a quencher, a hydrophobic resin, a surfactant, and a solvent) contained in the chemical solution, any known components can be used. Examples of the chemical include JP-A-2013-195844, JP-A-2016-057645, JP-A-2015-207006, WO2014 / 148241, JP-A-2016-188385, and JP-A-2016-188385. Components contained in the actinic ray-sensitive or radiation-sensitive resin composition described in JP-A-2017-219818 and the like can be mentioned.

<Use of chemicals>
The chemical is preferably used for manufacturing a semiconductor device. In particular, it is more preferably used for forming a fine pattern with a node of 10 nm or less (for example, a step including pattern formation using EUV).
The chemical solution has a pattern width and / or pattern interval of 17 nm or less (preferably 15 nm or less, more preferably 12 nm or less), and / or a resist having an obtained wiring width and / or wiring interval of 17 nm or less. A chemical solution used in the process (a pre-wet solution, a developing solution, a rinsing solution, a solvent for a resist solution, a stripping solution, etc.), in other words, a resist film having a pattern width and / or a pattern interval of 17 nm or less. It is particularly preferably used for the production of semiconductor devices produced using the same.

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 stripping liquid or the like. For example, it can be used for rinsing the edge line of the semiconductor substrate before and after the application of the resist.
Further, the above chemical solution can be used as a diluting solution of a resin contained in the resist solution and a solvent contained in the resist solution. Further, it may be diluted with another organic solvent and / or water.

In addition, the above chemical solution can be used for other uses other than the production of semiconductor devices, and can also be used as a developer for polyimide, a resist for sensors, a resist for lenses, and a rinsing solution.
Further, the above-mentioned chemical solution can be used as a solvent for medical use or cleaning use. In particular, it can be suitably used for cleaning containers, piping, substrates (eg, wafers, glass, and the like).

Among them, the chemical is selected from the group consisting of a developer, a rinse, a wafer cleaning liquid, a line cleaning liquid, a pre-wet liquid, a resist liquid, a lower layer film forming liquid, an upper layer film forming liquid, and a hard coat forming liquid. When used as a raw material of at least one liquid to be used, the effect is more exhibited.

(Chemical liquid manufacturing method)
The method for producing the chemical solution is not particularly limited, and a known production method can be used. Among them, the method for producing a chemical solution is preferable in that a chemical solution showing a better effect of the present invention is obtained, and the method for producing a chemical solution is performed by filtering a substance to be purified containing a solvent using a filter to obtain a chemical solution. .

(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 according to the embodiment of the present invention 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. Among them, 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, in that the number of particles (such as metal-containing particles) contained in the chemical solution is easily controlled in a desired range. The following is particularly preferred, and 3 nm or less is most preferred. The lower limit is not particularly limited, but is generally preferably 1 nm or more from the viewpoint of productivity.
In the present specification, the pore diameter and the pore diameter distribution of the filter are defined as isopropanol (IPA) or HFE-7200 (“Novec 7200”, manufactured by 3M, hydrofluoroether, C ₄ F ₉ OC _2). H ₅ ) means the pore size and pore size distribution determined by the bubble point.

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 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. 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, if an attempt is made to keep the flow rate of the object to be purified per unit time in the entire pipeline, a larger pressure is applied to the filter unit having a smaller pore size as compared with the filter unit having a larger pore size. There is. In this case, a pressure regulating valve, a damper, and the like are arranged between the filter units to make the pressure applied to the filter unit having a small pore diameter constant, or to connect a filter unit containing the same filter to a pipeline. It is preferable to increase the filtration area by, for example, arranging them in parallel along the line. This makes it possible to more stably control the number of particles in the chemical solution.

(Filter material)
The material for the filter is not particularly limited, and a known material 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.
Alternatively, 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 described later) may be used as the 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 material 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, and more preferably 50 ° or less. , 30 ° or less is particularly preferable.

As the chemical modification treatment, a method of introducing an ion exchange group into a substrate is preferable.
That is, as the filter, a filter in which each of the above-described materials is used as a base material and an ion exchange group is introduced into the base material is preferable. Typically, a filter including a layer containing a substrate containing an ion exchange group on the surface of the substrate is preferable. The surface-modified substrate is not particularly limited, and a filter in which an ion exchange group is introduced into the above polymer is preferable in terms of easier production.

Examples of the ion exchange group include a cation exchange group such as a sulfonic acid group, a carboxy group, and a phosphate group, and examples of the anion exchange group include a quaternary ammonium group. The method for introducing an ion-exchange group into a polymer is not particularly limited, and examples thereof include a method of reacting a compound containing an ion-exchange group and a polymerizable group with a polymer and typically grafting.

The method for introducing the ion-exchange group is not particularly limited, but the fibers of the above resin are irradiated with ionizing radiation (α-ray, β-ray, γ-ray, X-ray, electron beam, etc.) to form an active portion ( Radicals). The irradiated resin is immersed in a monomer-containing solution to graft-polymerize the monomer onto the substrate. As a result, a polymer is formed in which the monomer is bonded to the polyolefin fiber as a graft polymerization side chain. The resin containing the produced polymer as a side chain is contact-reacted with a compound containing an anion exchange group or a cation exchange group, and an ion exchange group is introduced into the graft-polymerized side chain polymer to give a final product. can get.

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 containing an ion-exchange group is used, the content of particles containing metal atoms in a chemical solution can be easily controlled in a desired range. The material of the filter containing 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.
The pore size of the filter containing an ion exchange group is not particularly limited, but is preferably 1 to 30 nm, more preferably 5 to 20 nm. The filter containing 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 terms of obtaining a drug solution exhibiting a superior effect of the present invention, the filtration step uses a filter containing 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 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 fiber membrane is on the primary side of the porous membrane, the surface energy of the fiber membrane is preferably higher than the polymer that 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.
The impurities contained in the filter include, for example, the above-described organic components. When the filtration step is performed using an unwashed filter (or a filter that has not been sufficiently washed), the content of the organic components in the chemical solution is reduced. The amount may exceed the permissible range for the liquid medicine of the present invention.
For example, when a polyolefin such as UPE and a polyfluorocarbon such as PTFE are used for a filter, the filter tends to contain an alkane having 12 to 50 carbon atoms as an impurity.
Also, when a polymer obtained by graft copolymerizing polyamide (nylon or the like) with polyamide such as nylon or polyimide, or polyolefin (UPE or the like) is used for the filter, the filter tends to contain an alkene having 12 to 50 carbon atoms as an impurity. .
The method of washing the filter includes, for example, a method of immersing the filter in an organic solvent having a low impurity content (for example, an organic solvent purified by distillation (eg, PGMEA)) for one week or more. In this case, the liquid temperature of the organic solvent is preferably 30 to 90 ° C.
The substance to be purified may be filtered using a filter whose degree of washing has been adjusted, and the resulting chemical solution may be adjusted so as to contain a desired amount of the organic component derived from the filter.

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

The material of the liquid contacting portion of the purification device used in the filtration step (meaning the material 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 (such as fluororesin) ) And at least one selected from the group consisting of electrolytically polished metal materials (such as stainless steel) (hereinafter 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 resin (for example, ethylene tetrafluoride resin, ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer, Hexafluoropropylene copolymer resin, ethylene tetrafluoride-ethylene copolymer resin, ethylene trifluoride ethylene-ethylene copolymer resin, vinylidene fluoride resin, ethylene trifluoride ethylene copolymer resin, and vinyl fluoride resin And the like, but not limited thereto.
Further, as the non-metallic material, a material which has been subjected to an antistatic treatment may be used from the viewpoint of preventing the chemical solution from being charged. As a method of performing the antistatic treatment, a method of using a conductive material together with the nonmetallic material (for example, the above-described fluororesin) is exemplified.
The conductive material preferably contains carbon. As carbon, carbon particles (for example, graphite, carbon black, acetylene black, Ketjen black) and carbon nanotubes (for example, a graphene sheet is formed into a single-layer or multi-layer coaxial tube from the viewpoint of further suppressing the charging of a chemical solution. And CNT.) And at least one material selected from the group consisting of carbon fibers.

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 (product name, the same applies hereinafter), Monel (product name, the same applies hereinafter), and Inconel (product 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), Hastelloy C-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 buff polishing is not particularly limited, but is preferably # 400 or less, more preferably 1,000 to # 400, and more preferably # 600 to # 400, since irregularities on the surface of the metal material are likely to be smaller. 400 is more preferred. Buff polishing is preferably performed before electrolytic polishing.
Further, the metal material may be subjected to an acid treatment and / or a passivation treatment. These treatments are preferably performed after electrolytic polishing.
Processing such as buffing, acid treatment, and passivation treatment may be performed alone or in combination of two or more.

<Other steps>
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 bringing the object to be purified into contact with the conductive material is preferably 0.001 to 60 seconds, more preferably 0.001 to 1 second, and particularly preferably 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 particularly 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.

〔container〕
The container contains the above-mentioned chemical solution. In order to prevent the chemical solution from flowing out of the container when storing or transporting the chemical solution container, the container in the chemical solution container is sealed with the medical solution stored therein.
The drug solution is stored in the container until use. When using the chemical, the chemical is taken out of the chemical container.

It is preferable that the container has a high degree of cleanness in the container and a small amount of elution of impurities for use in manufacturing semiconductor devices.
Specific examples of the container include, but are not limited to, a “clean bottle” series manufactured by Aicello Chemical Co., Ltd. and a “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.

少なくとも At least a part of the liquid contact part of the container may be a corrosion-resistant material (preferably, electropolished stainless steel or fluororesin) 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.

As a preferred embodiment of the container, there is an embodiment in which at least a part of the liquid contact part of the container is stainless steel which is electropolished. In this case, the average surface roughness Ra of the liquid contacting part of the container is preferably 1500 nm or less, and is more excellent in suppressing defects of the chemical solution, and is preferably less than 100 nm, more preferably 10 nm or less from the viewpoint that the charging of the chemical solution can be further suppressed. Preferably, less than 5 nm is more preferred. Note that the lower limit of the average surface roughness Ra of the liquid contact part of the container is preferably 1 nm or more.
Here, the average surface roughness Ra of the liquid contact part of the container can be measured as follows. First, the surface shape is measured with an atomic force microscope (AFM) using a cantilever having a probe diameter of 10 nm to obtain three-dimensional data. Here, the liquid-contact part of the container was cut into a size of 1 cm square, set on a horizontal sample stage on a piezo scanner, approached the cantilever to the sample surface, and reached XY In this case, the unevenness of the sample is captured by the displacement of the piezo in the Z direction. At the time of measurement, 512 × 512 points are measured in a range of 5 μm × 5 μm on the surface. The average surface roughness Ra is determined using the three-dimensional data (f (x, y)) determined above.

As a preferred embodiment of the container, there is an embodiment in which at least a part of the liquid contact part of the container further contains a conductive material together with the above-described fluororesin. Thereby, the charging of the chemical solution is further suppressed. Specific examples of the conductive material are the same as the conductive material in the corrosion-resistant material described above.

The porosity in the container of the liquid medicine container is preferably 50 to 99.99% by volume, more preferably 50 to 99.90% by volume, and particularly preferably 80 to 99% by volume. If the porosity is within the above range, the chemical solution can be easily handled because there is an appropriate space.
The porosity is calculated according to the following equation (X).
Formula (X): Porosity (% by volume) = {1− (volume of drug solution in container / volume of container in container)} × 100
The container volume is synonymous with the internal volume (capacity) of the container.

A gas containing an organic compound (specific organic compound B described later) having a higher ClogP value than the solvent is present in the cavity of the container in the chemical solution container.
The gas is usually air, but it is preferable that at least a part of the air is replaced by nitrogen gas. If at least a part of the air is replaced with nitrogen gas, the content of the organic compound B present in the voids can be controlled, so that a chemical solution having excellent defect suppression performance can be obtained.
The content of nitrogen gas is preferably from 95 to 99.9999% by volume, more preferably from 97 to 99.99% by volume, based on the total volume of the void portion of the container, from the viewpoint that the effect of the present invention is more exhibited. .

<Specific organic compound B>
The gas present in the cavity of the container contains the specific organic compound B. As described above, the specific organic compound B is an organic compound having a higher ClogP value than the solvent in the chemical solution.
Preferred embodiments and specific examples of the ClogP value of the specific organic compound B are the same as those of the specific organic compound A.

The total content of the specific organic compound A and the specific organic compound B is 100,000 mass ppt or less, preferably 0.1 to 100,000 mass ppt, based on the total mass of the drug solution.
When the total of the above contents is 100,000 mass ppt or less, the specific organic compound itself can be prevented from becoming a defect, so that a chemical solution having excellent defect suppression performance can be obtained.
Further, when the total content is 0.1 mass ppt or more, generation of defects due to metal-containing particles can be suppressed by the action of the specific organic compound. Although the details of this reason are not clear, it is speculated that the metal-containing particles aggregate or the metal-containing particles remain on the wiring board because the specific organic compound in the chemical solution suppresses the aggregation. . This effect is particularly prominent when the fine pattern is formed.
The upper limit of the total of the above contents is preferably 100,000 mass ppt or less, more preferably 2,000 mass ppt or less, still more preferably 1,000 mass ppt or less, from the viewpoint that the above effect is more exhibited. Particularly preferred is a mass ppt or less.
The lower limit of the total content is preferably 0.1 mass ppt or more from the viewpoint that the above effects are more exhibited.

含有 The content and type of the specific organic compound B in the gas can be measured using GCMS (gas chromatography mass spectrometer; gas chromatography mass spectrometry).

The content of the specific organic compound B is preferably 50,000 mass ppt or less, more preferably 0.05 to 50,000 mass ppt, and more preferably 0.05 to 50,000 mass ppt, based on the total mass of the chemical solution, from the viewpoint of more excellent defect suppression performance. 05 to 500 mass ppt is more preferable, and 0.05 to 5 mass ppt is particularly preferable.

The mass ratio of the total content of the specific organic compound A and the specific organic compound B to the content of the metal-containing particles [(specific organic compound A + specific organic compound B) / metal-containing particles] is 0.01 to 100,000. Is preferably 0.1 or more, more preferably 10,000 or less, and particularly preferably 1,000 or less.
When the mass ratio is 0.01 or more, generation of defects due to metal-containing particles can be suppressed by the action of the specific organic compound. Although the details of this reason are not clear, it is speculated that the metal-containing particles aggregate or the metal-containing particles remain on the wiring board because the specific organic compound in the chemical solution suppresses the aggregation. . This effect is particularly prominent when the fine pattern is formed.
When the mass ratio is 100,000 or less, the specific organic compound itself can be prevented from becoming a defect, or the generation of composite particles of the specific organic compound and the metal-containing particles can be suppressed. A chemical solution is obtained.

The mass ratio of the content of the specific organic compound A to the content of the specific organic compound B (specific organic compound A / specific organic compound B) is preferably 1 or more, more preferably 10 or more, and particularly preferably 1,000 or more. .
When the mass ratio is 1 or more, the defect suppression performance over time (that is, the defect suppression performance when the drug solution is used after storing the drug solution container for a long time) is excellent.
The upper limit of the mass ratio is not particularly limited, but is often 10,000 or less.

Preferred embodiments of the type of the specific organic compound B are the same as those of the specific organic compound A, and among them, a phthalic acid ester is preferable, and is selected from the group consisting of dioctyl phthalate (DOP) and diisononyl phthalate (DINP). At least one is preferred.
When the present drug solution container contains DOP and DINP, the mass ratio of the DOP content to the DINP content (DOP / DINP) in the present drug solution container is preferably 1 or more, more preferably 5 or more. Since DINP has a higher boiling point than DOP, it is considered that when it adheres to a silicon substrate, it is more likely to remain as a defect. Therefore, when the mass ratio is 1 or more, a medicinal solution having more excellent defect suppression performance can be obtained.
The upper limit of the mass ratio (DOP / DINP) is not particularly limited, but is preferably 10,000 or less, more preferably 1,000 or less.

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. In order to improve the measurement accuracy, in the measurement of the content of organic components and the content of metal components, when measuring components below the detection limit in normal measurement, concentrate the drug solution and perform the measurement. The concentration was converted to the concentration of the solution before concentration, and the content was calculated.

[Chemical solution]
〔filter〕
Each of the filters used for purifying the chemical solution was a filter that was washed using a washing solution obtained by distilling and purifying commercially available PGMEA (propylene glycol monomethyl ether acetate). In the immersion, the entire filter unit including the filter was immersed in PGMEA, and all the liquid contact parts were washed. The cleaning period was set to one week or more. During the washing, the temperature of the PGMEA was maintained at 30 ° C.
The following filters were used as filters.
・ UPE: Ultra high molecular weight polyethylene filter, Entegris, 3 nm pore size
・ PTFE: Polytetrafluoroethylene filter, Entegris, pore size 10 nm
・ Nylon: Nylon filter, manufactured by PALL, pore size 5nm
・ Nylon graft UPE: Nylon / ultra high molecular weight polyethylene graft copolymer filter, Entegris, 3 nm pore size
・ Polyimide: Polyimide filter, manufactured by Entegris, pore size 10 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. Commercially available products were used for the following organic solvents. However, in the following “PGMEA / PGME (7: 3)” and “PGMEA / PC (9: 1)”, organic solvents before mixing were purchased, and predetermined amounts were mixed with each other to obtain purified materials.
PGMEA: propylene glycol monomethyl ether acetate, ClogP value = 0.56)
CHN: cyclohexanone, ClogP value = 0.81
-NBA: butyl acetate, ClogP value = 1.78
NMP: N-methyl-2-pyrrolidone, ClogP value = -0.38
MIBC: 4-methyl-2-pentanol, ClogP value = 1.31
PGMEA / PGME (7: 3): 7: 3 (v / v) mixture of PGMEA and PGME (propylene glycol monomethyl ether, ClogP value = 0.20) PGMEA / PC (9: 1): PGMEA 9: 1 (v / v) mixed solution of PC and propylene carbonate (ClogP value = −0.41). IAA: isoamyl acetate, ClogP value = 2.3.
EL: ethyl lactate, ClogP value = 0.04
-Propylene glycol monomethyl ether, ClogP value = -0.20
-Propylene glycol monopropyl ether, ClogP value = 0.81
-Methyl methoxypropionate, ClogP value = 0.26
・ Cyclopentanone, ClogP value = 0.24
-Γ-butyrolactone, ClogP value = -0.64
・ Diisoamyl ether, ClogP value = 3.8
-Isopropanol, ClogP value = 0.05
-Dimethyl sulfoxide, ClogP value = -1.35
・ Diethylene glycol, ClogP value = −0.95
-Ethylene glycol, ClogP value = -0.79
・ Dipropylene glycol, ClogP value = −0.31
-Propylene glycol, ClogP value = -0.92
・ Ethylene carbonate, ClogP value = -0.27
-Sulfolane, ClogP value = -0.78
-Cycloheptanone, ClogP = 1.48
-2-heptanone, ClogP value = 1.91
Butyl butyrate, ClogP value = 1.78
-Isobutyl isobutyrate, ClogP value = 4.4
-Undecane, ClogP value = 6.5
Pentyl propionate, ClogP value = 2.8
-Isopentyl propionate, ClogP value = 2.70
-Ethylcyclohexane, ClogP value = 4.4
・ Mesitylene, ClogP value = 3.6
-Decane, ClogP value = 6.0

(Purification treatment)
One selected from the above-mentioned purified products was distilled, and the purified purified product was passed through the above-mentioned washed filter one or more times to perform purification.
In the course of a series of purifications, a stainless steel pipe whose liquid contact part was electropolished or a stainless steel pipe that was not electropolished was used as a pipe for transferring the object to be purified and the chemical solution.
The type of material to be purified, the type of filter, the cleaning period of the filter, the number of passages, the type of piping, and the length of piping (distance of transfer by piping) are appropriately changed, and are shown in Tables 1 and 2, respectively. The chemical solution shown was used.

[container]
As a container for storing the chemical solution, a container having a liquid contact part made of a material shown in Table 1 or Table 2 was used.
-PFA: perfluoroalkoxy alkane-PTFE: polytetrafluoroethylene-SUS316L-EP: austenitic stainless steel (with electrolytic polishing)
・ HDPE: High density polyethylene ・ SUS304-EP: Austenitic stainless steel (with electrolytic polishing)
・ SUS304: Austenitic stainless steel (no electrolytic polishing)
-Glass-PTFE and CNT: Materials containing polytetrafluoroethylene and carbon nanotubes-PTFE and carbon particles: Materials containing polytetrafluoroethylene and carbon particles-PTFE and carbon fibers: Materials containing polytetrafluoroethylene and carbon fibers

In addition, about some Examples in Table 2, as SUS316L-EP, buff polishing (polishing abrasive size: # 400) in pre-treatment of electrolytic polishing and / or acid treatment (post-treatment of electrolytic polishing) The wetted portion was washed with a 7% by mass dilute nitric acid solution).

{Circle around (2)} For the containers shown in Table 2, the average surface roughness Ra of the liquid-contacting portions of the containers was measured by the method described above.

First, a container is placed in a vacuum desiccator having a capacity of 1,000 liters, and components that may come into contact with a chemical solution such as a vacuum desiccator, a liquid contact portion of the container, and a pipe for flowing a chemical solution into the container are manufactured using a semiconductor grade. Then, the air in the vacuum desiccator was replaced with nitrogen gas and dried.
Next, a process in which the inside of the vacuum desiccator was evacuated and then filled with nitrogen gas was repeatedly performed to make the atmosphere in the vacuum desiccator clean.

[Chemical container]
The chemical solution purified as described above was accommodated in a container placed in a vacuum desiccator that had been cleaned as described above so that the porosity of the container became a value shown in Tables 1 and 2. Then, the container was hermetically sealed so that the drug solution in the container did not flow out, and a drug solution container was obtained.

[Measurement of content of each component in chemical solution container]
The following methods were used to measure the content of each component and the like in the drug solution container. In addition, the following measurements were all performed in a clean room of a level satisfying ISO (International Organization for Standardization) class 2 or less. In order to improve the measurement accuracy, in the measurement of each component, when the measurement is below the detection limit in normal measurement, the concentration is reduced to 1/100 in terms of volume, and the measurement is performed. The content was calculated. The results are collectively shown in Tables 1 and 2.
The measurement of the content of each component in the chemical solution container was performed immediately after the production (meaning immediately after the chemical solution was stored in the container and the chemical solution was sealed).

(Organic compound)
The content of the organic compound (specific organic compound A) having a ClogP value higher than that of the organic solvent in each chemical solution was determined using a gas chromatograph mass spectrometer (product name "GCMS-2020", manufactured by Shimadzu Corporation), and the measurement conditions were as follows: ).
Further, the content of an organic compound (specific organic compound B) having a ClogP value higher than that of the organic solvent contained in the gas present in the void portion of the chemical solution container was also measured using the gas chromatograph mass spectrometer.

<Measurement conditions>
Capillary column: InertCap 5MS / NP 0.25 mmI. D. × 30m df = 0.25 μm
Sample introduction method: Split 75 kPa constant pressure vaporization chamber temperature: 230 ° C
Column oven temperature: 80 ° C (2 min) -500 ° C (13 min) Heating rate 15 ° C / min
Carrier gas: helium septum purge flow rate: 5 mL / min
Split ratio: 25: 1
Interface temperature: 250 ° C
Ion source temperature: 200 ° C
Measurement mode: Scan m / z = 85-500
Sample introduction volume: 1 μL

Based on the content (concentration) of the specific organic compound A in the drug solution and the content (concentration) of the specific organic compound B in the gas measured as described above, the mass of the specific organic compound A in the drug solution container , And the mass of the specific organic compound B in the drug solution container was calculated.
Then, a ratio of the mass of the specific organic compound A in the chemical solution container to the mass of the chemical solution in the chemical solution container (that is, “the content (mass ppm) of the specific organic compound A with respect to the total mass of the chemical solution”) ) Were calculated, and numerical values are shown in the column of “content of specific organic compound A” in Tables 1 and 2.
Similarly, the ratio of the mass of the specific organic compound B in the chemical solution container to the mass of the chemical solution in the chemical solution container (that is, the “content (mass ppm) of the specific organic compound B with respect to the total mass of the chemical solution”) ) Was calculated, and numerical values are shown in the column of “content of specific organic compound B” in Tables 1 and 2.
The “total content of the specific organic compound A and the specific organic compound B” in Tables 1 and 2 is the “content of the specific organic compound A” and the “content of the specific organic compound B” in Tables 1 and 2. Amount ".
Similarly, the specific organic compound A1 having a ClogP value of 6 or more among the specific organic compounds A and the specific organic compound B1 having a ClogP value of 6 or more among the specific organic compounds B with respect to the total mass of the drug solution are included. The sum of the amounts (mass ppt) was determined. The results are shown in Tables 1 and 2 in the column of "Total amount of specific organic compounds having a ClogP value of 6 or more".
Similarly, the total (mass ppt) of the contents of the phthalate ester of the specific organic compound A and the phthalate ester of the specific organic compound B with respect to the total mass of the chemical solution was determined. The results are shown in Table 1 and Table 2 in the column of "Total amount of phthalate".
Similarly, the sum of the contents of dioctyl phthalate (DOP) and diisononyl phthalate (DINP) of the specific organic compound A and DOP and DINP of the specific organic compound B with respect to the total mass of the chemical solution ( Mass (ppt) was determined. The results are shown in “Total content (mass ppt)” in the column “DINP and DOP” in Tables 1 and 2.

Further, the mass ratio of the content (mass) of the specific organic compound B in the drug solution container to the content (mass) of the specific organic compound A in the drug solution container was calculated. The results are shown in the columns of "mass ratio of specific organic compound A and specific organic compound B" in Tables 1 and 2.
Further, the mass ratio of the content (mass) of DOP in the drug solution container to the content (mass) of DINP in the drug solution container was calculated. The results are shown in “Content ratio DOP / DINP” in the column of “DINP and DOP” in Tables 1 and 2.

(Metal-containing particles)
The content of the metal-containing particles in the chemical solution was measured by a method using SP-ICP-MS.
The equipment used is as follows. The results are shown in Tables 1 and 2.
・ Manufacturer: PerkinElmer
・ Model: NexION350S
The following analysis software was used for the analysis.
・ "SP-ICP-MS" Syngistix Nano Application Module

Also, the mass ratio of the total content of the specific organic compound A and the specific organic compound B in the chemical solution container to the content (mass) of the metal-containing particles in the chemical solution was calculated. The results are shown in Table 1 and Table 2 in the column of "content ratio of metal-containing particles to specific organic compound".

(Metal nanoparticles)
The number of particles of metal nanoparticles (metal-containing particles having a particle diameter of 0.5 to 17 nm) in the chemical solution was measured by the following method.
First, a predetermined amount of a chemical was applied on a silicon substrate to form a substrate with a chemical layer, and the surface of the substrate with the chemical layer was scanned with laser light to detect scattered light. Thereby, the position and the particle size of the defect existing on the surface of the substrate with the chemical solution layer were specified. Next, based on the position of the defect, elemental analysis was performed by EDX (energy dispersive X-ray) analysis to examine the composition of the defect. By this method, the number of metal nanoparticles on the substrate was determined, and converted into the number of particles contained per unit volume of the chemical solution (particles / cm ³ ).
In the analysis, a combination of a wafer inspection apparatus “SP-5” manufactured by KLA-Tencor and a fully automatic defect review and classification apparatus “SEMVion G6” manufactured by Applied Materials was used.
Further, a sample in which particles having a desired particle size could not be detected due to the resolution of the measuring device or the like was detected using the method described in paragraphs 0015 to 0067 of JP-A-2009-188333. That is, on a substrate, a SiO _X layer is formed by CVD (chemical vapor deposition) method, then, to form a chemical layer to cover the layer above. Next, the composite layer having the SiO _X layer and the chemical solution layer applied thereon is dry-etched, and the obtained protrusion is irradiated with light to detect scattered light. The method of calculating the volume of the protrusion and calculating the particle diameter of the particle from the volume of the protrusion was used.

[Evaluation of defect suppression performance]
The chemical solution was taken out from the medical solution container, and this was used as a pre-wet liquid, and the defect suppression performance was evaluated.
Here, the defect suppression performance used the chemical solution immediately after manufacturing the chemical solution container (meaning immediately after the chemical solution was stored in the container and the chemical solution was sealed. In the table, it was indicated as “immediately after storage”). The test was performed for both the case and the case where the drug solution was used after storing the drug solution container at 50 ° C. for one year (indicated as “aging” in the table).
In addition, the resist composition used is as follows.

[Resist composition 1]
The resist composition 1 was obtained by mixing each component with the following composition.
・ Resin (A-1): 0.77 g
・ Acid generator (B-1): 0.03 g
-Basic compound (E-3): 0.03 g
・ PGMEA: 67.5 g
・ EL: 75g

<Resin (A), etc.>
(Synthesis Example 1) Synthesis of Resin (A-1) Cyclohexanone (600 g) was placed in a 2 L flask, and the atmosphere was replaced with nitrogen at a flow rate of 100 mL / min for 1 hour. Thereafter, 4.60 g (0.02 mol) of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the temperature was raised until the internal temperature reached 80 ° C. Next, the following monomer and 4.60 g (0.02 mol) of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 200 g of cyclohexanone to prepare a monomer solution. The monomer solution was dropped into the flask heated to 80 ° C. over 6 hours. After the completion of the dropwise addition, the reaction was further performed at 80 ° C. for 2 hours.
48.66 g (0.3 mol) of 4-acetoxystyrene
109.4 g (0.6 mol) of 1-ethylcyclopentyl methacrylate
Monomer 1 22.2 g (0.1 mol)

(4) The reaction solution was cooled to room temperature and dropped into 3 L of hexane to precipitate a polymer. The filtered solid was dissolved in 500 mL of acetone, dropped again into 3 L of hexane, and the filtered solid was dried under reduced pressure to obtain 160 g of 4-acetoxystyrene / 1-ethylcyclopentyl methacrylate / monomer 1 copolymer (A-1). Was.

１０ 10 g of the polymer obtained above, 40 mL of methanol, 200 mL of 1-methoxy-2-propanol, and 1.5 mL of concentrated hydrochloric acid were added to a reaction vessel, and the mixture was heated to 80 ° C. and stirred for 5 hours. The reaction solution was allowed to cool to room temperature and dropped into 3 L of distilled water. The filtered solid was dissolved in 200 mL of acetone, dropped again into 3 L of distilled water, and the filtered solid was dried under reduced pressure to obtain a resin (A-1) (8.5 g). The weight average molecular weight (Mw) in terms of standard polystyrene measured by gel permeation chromatography (GPC) (solvent: THF (tetrahydrofuran)) was 11,200, and the molecular weight dispersity (Mw / Mn) was 1.45. The structure and the like of the resin A-1 are shown below.

<Photoacid generator (B)>
The following were used as the photoacid generator.

<Basic compound (E)>
The following were used as basic compounds.

(Residue defect suppression performance, bridge defect suppression performance, and spot-like defect suppression performance)
The residue defect suppression performance, the bridge defect suppression performance, and the spot defect suppression performance of the chemical solution were evaluated by the following methods. In the test, a coater / developer “LITHIUS (registered trademark) Pro Z” manufactured by Tokyo Electron Limited was used.
First, AL412 (manufactured by Brewer Science) was applied on a silicon wafer and baked at 200 ° C. for 60 seconds to form a resist underlayer film having a thickness of 20 nm. A pre-wet solution (chemical solution 1) was applied thereon, and a resist composition 1 was applied thereon, and baked (PB: Prebake) at 100 ° C. for 60 seconds to form a resist film having a thickness of 30 nm.

This resist film was coated with a reflective mask having a pitch of 20 nm and a pattern width of 15 nm using an EUV exposure machine (manufactured by ASML; NXE3350, NA 0.33, Dipole 90 °, outer sigma 0.87, inner sigma 0.35). Exposure via Thereafter, heating was performed at 85 ° C. for 60 seconds (PEB: Post Exposure Bake). Next, the film was developed with an organic solvent-based developer for 30 seconds and rinsed for 20 seconds. Subsequently, the wafer was rotated at a rotation speed of 2000 rpm for 40 seconds to form a line-and-space pattern having a pitch of 20 nm and a pattern line width of 15 nm.

An image of the above pattern is obtained, and the obtained image is used in combination with a wafer inspection apparatus “SP-5” manufactured by KLA-Tencor and a fully automatic defect review and classification apparatus “SEMVion G6” manufactured by Applied Materials. The number of residues in the unexposed area per unit area was measured.
The sample in which particles having a desired particle size could not be detected due to the resolution of the measuring device or the like was detected using the method described in paragraphs 0015 to 0067 of JP-A-2009-188333. That is, on a substrate, a SiO _X layer is formed by CVD (chemical vapor deposition) method, then, to form a chemical layer to cover the layer above. Next, the composite layer having the SiO _X layer and the chemical solution layer applied thereon is dry-etched, and the obtained protrusion is irradiated with light to detect scattered light. The method of calculating the volume of the protrusion and calculating the particle diameter of the particle from the volume of the protrusion was used.
The results were evaluated according to the following criteria, and are shown in Tables 1 and 2.

A: The number of defects was less than 60.
B: The number of defects was 60 or more and less than 90.
C: The number of defects was 90 or more and less than 120.
D: The number of defects was 120 or more and less than 150.
E: The number of defects was 150 or more and less than 180.

(Charge amount)
The amount of charge on the liquid surface immediately after filling with the chemical solution was measured using a digital electrostatic potential meter KSD-2000 manufactured by Kasuga Electric Co., Ltd. The results were evaluated according to the following criteria and are shown in Table 2.
A: The charge amount was within the range of ± 2 kV.
B: The charge amount was out of the range of ± 2 kV and was in the range of ± 10 kV.
C: The charge amount was out of the range of ± 10 kV.

In Tables 1 and 2, the numerical values in the column of “the number of particles contained in metal nanoparticles” are abbreviations of exponential notation. For example, “1.00E + 05” is “1.00 × 10 ⁵ ”. Means

As shown in Table 1 and Table 2, the content of the metal-containing particles is 10 mass ppt or less based on the total mass of the chemical solution, and the total content of the specific organic compound A and the specific organic compound B is the total amount of the chemical solution. When the mass was 100,000 mass ppt or less with respect to the mass, the defect suppression performance was excellent even when the chemical solution taken out immediately after the storage in the chemical solution container or after long-term storage was used (Example).
Further, from the comparison between Examples 1 and 2 and Example 7, if the content of the metal-containing particles is in the range of 0.1 to 10 mass ppt with respect to the total mass of the chemical solution (Examples 1 and 2) In addition, it was shown that the use of the chemical solution taken out immediately after the chemical solution was stored in the chemical solution container or after long-term storage was superior to the defect suppression performance.
Also, from the comparison between Example 3 and Example 19, if the content of the metal-containing particles is 1 mass ppt or less with respect to the total mass of the chemical solution (Example 19), the content immediately after the storage in the chemical solution container and the long term It was shown that the use of the chemical taken out at any time after the storage was superior to the defect suppression performance.
From the comparison between Example 4 and Example 19, if the total content of the specific organic compound A and the specific organic compound B is 2,000 mass ppt or less with respect to the total mass of the chemical solution (Example 19) ), It was shown that the use of the chemical solution taken out immediately after storage in the chemical solution container or after long-term storage was superior to the defect suppression performance.
From the comparison between Example 5 and Example 19, if the total mass ratio of the specific organic compound A and the specific organic compound B to the content of the metal-containing particles is 0.1 or more ( Example 19) It was shown that the use of the chemical solution taken out at least one of the timing immediately after the storage in the chemical solution container and after the long-term storage showed superior defect suppression performance.
From the comparison between Example 6 and Example 19, if the total mass ratio of the specific organic compound A and the specific organic compound B to the content of the metal-containing particles is 100,000 or less ( Example 19), it was shown that the use of the chemical solution taken out immediately after the chemical solution was stored in the chemical solution container or after long-term storage was superior to the defect suppression performance.
Also, from the comparison between Example 8 and Example 11, when the mass ratio of the specific organic compound B to the specific organic compound A is 1 or more (Example 11), the chemical solution taken out after long-term storage is more excellent in suppressing defects. It was shown that.
Also, from the comparison of Examples 9 to 12, when the porosity of the container in the chemical solution container is in the range of 50 to 99.99% by volume (Examples 9 and 11), the defect suppression performance of the chemical solution taken out after long-term storage. Was shown to be better.
From the comparison between Example 15 and Example 16, if the mass ratio of the content of dioctyl phthalate to the content of diisononyl phthalate (DOP / DINP) is 1 or more (Example 15), the chemical solution container was used. When the chemical solution taken out after long-term storage was used, it was shown to be more excellent in defect suppression performance.

As shown in Table 2, from the comparison of Examples 102 to 106, when the liquid contact portion of the container is stainless steel that has been electropolished, the average surface roughness Ra of the liquid contact portion of the container is less than 100 nm. And the defect suppression performance was excellent (Example 102).
As shown in Table 2, from the comparison between Example 101 and Examples 107 to 109, when the liquid contact part containing the conductive material together with the fluororesin was used, the charging of the chemical solution could be further suppressed.

On the other hand, as shown in Table 1, when the content of the metal particles in the chemical solution or the total content of the specific organic compound A and the specific organic compound B is out of the above range, immediately after storage in the chemical solution container and for a long time, Defect suppression performance was inferior regardless of the chemical solution taken out at any time after storage (Comparative Example).

(Example 34)
The PGMEA used in Example 15 was subjected to repeated distillation and filtration to prepare a drug solution having a specific organic compound content of less than 0.1 mass ppt.
8000 mass ppt of dibutyl phthalate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to this solution, and the solution obtained by repeating the filtration again was contained in a container (the same container as in Example 15). 34 chemical solution containers were obtained. In the drug solution container of Example 34, the content of the specific organic compound A composed of dibutyl phthalate was 4,800 mass ppt, and the content of the specific compound B composed of dibutyl phthalate was 10 mass ppt.
The same evaluation as in Example 15 was performed using the liquid medicine stored in the liquid medicine container of Example 34, and the defect suppression performance after storing the liquid medicine container at 50 ° C. for one year was evaluated as “C”. Except for the above, the same results as in Example 15 were obtained.

Claims

A container, and a liquid medicine stored in the container, a liquid medicine container,
The chemical solution contains a solvent, metal-containing particles containing a metal atom, and an organic compound having a higher ClogP value than the solvent,
The content of the metal-containing particles is 10 mass ppt or less with respect to the total mass of the chemical solution,
A gas containing an organic compound having a higher ClogP value than the solvent is present in the cavity of the container, and the total content of the organic compound in the gas and the organic compound in the chemical solution is the total mass of the chemical solution. Liquid medicine container having a mass of 100,000 mass ppt or less.
The content of the metal-containing particles is 0.001 to 10 mass ppt, based on the total mass of the chemical solution;
2. The chemical solution according to claim 1, wherein the total content of the organic compound in the gas and the organic compound in the chemical solution is 0.1 to 100,000 mass ppt based on the total mass of the chemical solution. Container.
3. The method according to claim 1, wherein a total mass ratio of the content of the organic compound in the gas and the content of the organic compound in the chemical solution to the content of the metal-containing particles is 0.01 to 100,000. The liquid medicine container according to the above.
4. The chemical solution container according to claim 1, wherein each of the organic compound in the gas and the organic compound in the chemical solution has a ClogP value of 6 or more.
The chemical solution container according to any one of claims 1 to 4, wherein both the organic compound in the gas and the organic compound in the chemical solution contain a phthalate ester.
The chemical solution container according to claim 5, wherein the phthalic acid ester includes at least one selected from the group consisting of dioctyl phthalate and diisononyl phthalate.
The chemical solution container according to claim 6, wherein the mass ratio of the dioctyl phthalate content to the diisononyl phthalate content is 1 or more.
8. The chemical solution container according to claim 1, wherein a mass ratio of the content of the organic compound in the chemical solution to the content of the organic compound in the gas is 1 or more.
薬 The chemical solution container according to any one of claims 1 to 8, wherein the solvent is an organic solvent.
The organic solvent is cyclohexanone, butyl acetate, N-methyl-2-pyrrolidone, 4-methyl-2-pentanol, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene carbonate, isoamyl acetate, propylene glycol Monomethyl ether, propylene glycol monopropyl ether, methyl methoxypropionate, cyclopentanone, γ-butyrolactone, diisoamyl ether, isopropanol, dimethyl sulfoxide, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, sulfolane, cyclohepta Non-, 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, Acid isopentyl, ethylcyclohexane, is at least one selected from the group consisting of mesitylene, and decane, chemical container according to claim 9.
In the metal-containing particles, the number of metal nanoparticles having a particle diameter of 0.5 to 17 nm per unit volume of the chemical solution is 1.0 × 10 1 to 1.0 × 10 9 / cm 3 . The drug solution container according to any one of claims 1 to 10.
The gas includes nitrogen gas,
The content of the nitrogen gas is 95 to 99.9999% by volume based on the total volume of the voids;
12. The chemical solution container according to claim 1, wherein the content of the organic compound in the gas is 0.05 to 50,000 mass ppt based on the total mass of the chemical solution.
The medical solution container according to any one of claims 1 to 12, wherein the porosity of the container in the medical solution container is 50 to 99.99% by volume.
(14) The chemical solution container according to any one of (1) to (13), wherein at least a part of the liquid contact part of the container is made of fluororesin, electrolytically polished stainless steel, or glass.
When at least a part of the liquid contact part of the container is the electropolished stainless steel,
The liquid medicine container according to claim 14, wherein the liquid contact part of the container has an average surface roughness Ra of less than 100 nm.
The liquid medicine container according to claim 14, wherein at least a part of the liquid contact part of the container further includes a conductive material together with the fluororesin.
17. The chemical solution container according to claim 16, wherein the conductive material contains carbon.
The chemical solution container according to claim 17, wherein the carbon is at least one selected from the group consisting of carbon particles, carbon nanotubes, and carbon fibers.
At least one selected from the group consisting of a developer, a rinse, a wafer cleaning liquid, a line cleaning liquid, a pre-wet liquid, a resist liquid, a lower layer film forming liquid, an upper layer film forming liquid, and a hard coat forming liquid; The medical solution container according to any one of claims 1 to 18, which is used as a raw material of the liquid.