TWI902672B - Chemical liquid housing - Google Patents

Abstract

The present invention addresses the problem of providing a liquid containment body for a liquid with excellent containment defect suppression performance. The liquid containment body of the present invention comprises a container and a liquid contained within the container. The liquid contains a solvent, metal-containing particles containing metal atoms, and organic compounds with a ClogP value higher than that of the solvent. The content of the metal-containing particles relative to the total mass of the liquid is less than 10 mass ppt. A gas containing organic compounds with a ClogP value higher than that of the solvent is present in the voids of the container. The total content of the organic compounds in the gas and the organic compounds in the liquid is less than 100,000 mass ppt relative to the total mass of the liquid.

Description

Drug container

This invention relates to a container for a pharmaceutical liquid.

When manufacturing semiconductor devices using a wiring process incorporating photolithography, solutions containing water and/or organic solvents can be used as pre-wetting solutions, photoresist, developer, rinsing solutions, stripping solutions, chemical mechanical polishing (CMP) slurries, and post-CMP cleaning solutions.

After manufacturing, the liquid medicine is contained in a container and stored in this container form for a certain period of time before being removed and used.

As a container for such liquid solutions, Patent Document 1 describes "a glass container for use with phenolic varnish resin-based positive photoresist, characterized in that its inner surface is treated with fluoride gas and sulfurous acid gas under heating, and that it contains an organic solvent-based phenolic varnish resin-based positive photoresist solution."

[Previous Technical Documents] [Patent Documents]

[Patent Document 1] Japanese Patent Application Publication No. 11-029148

Sometimes, impurities in the chemical solution can cause defects in semiconductor devices. These defects can lead to reduced manufacturing yields and electrical malfunctions such as short circuits.

The inventors removed the liquid from the liquid container and applied it to a wiring formation step involving photolithography. The results showed that defects sometimes occurred on the wiring substrate.

The problem of this invention is to provide a liquid containment body for a liquid with excellent containment defect suppression performance.

The inventors, through in-depth research into the aforementioned problem, discovered the following and thus completed this invention: a liquid containing metal particles within a specified range is contained within a liquid container. As long as the total content of organic compounds in the liquid and the content of organic compounds present in the pores of the container, relative to the total mass of the liquid, is within a specified range, a liquid with excellent defect suppression performance can be obtained.

In other words, the inventors have discovered that the above-mentioned problems can be solved by the following configuration.

[1]

A pharmaceutical liquid container includes a container and a pharmaceutical liquid contained within the container. The pharmaceutical liquid contains a solvent, metal-containing particles containing metal atoms, and an organic compound with a ClogP value higher than that of the solvent. The content of the metal-containing particles is less than 10 ppt by mass relative to the total mass of the pharmaceutical liquid. A gas containing the organic compound with a ClogP value higher than that of the solvent is present in the pores of the container. The total content of the organic compound in the gas and the organic compound in the pharmaceutical liquid is less than 100,000 ppt by mass relative to the total mass of the pharmaceutical liquid.

[2]

The liquid container as described in [1] contains particles of the aforementioned metal in an amount of 0.001 to 10 ppm relative to the total mass of the liquid, and the total content of the aforementioned organic compounds in the gas and the aforementioned organic compounds in the liquid is 0.1 to 100,000 ppm relative to the total mass of the liquid.

[3]

The pharmaceutical container as described in [1] or [2], wherein the mass ratio of the total content of the aforementioned organic compounds in the gas and the aforementioned organic compounds in the pharmaceutical liquid to the content of the aforementioned metal-containing particles is 0.01 to 100,000.

[4]

The liquid medicine container as described in any of [1] to [3], wherein the ClogP value of both the organic compound in the gas and the organic compound in the liquid medicine is 6 or higher.

[5]

The liquid container as described in any of [1] to [4], wherein the organic compounds in the gas and the organic compounds in the liquid both contain phthalates.

[6]

The liquid container as described in [5] contains, wherein the phthalate comprises at least one selected from the group consisting of dioctyl phthalate and diisononyl phthalate.

[7]

The liquid container as described in [6] contains a drug solution in which the mass ratio of the content of dioctyl phthalate to the content of diisononyl phthalate is 1 or more.

[8]

The liquid container as described in any one of [1] to [7], wherein the mass ratio of the content of the aforementioned organic compound in the liquid to the content of the aforementioned organic compound in the gas is 1 or more.

[9]

The liquid container as described in any of [1] to [8], wherein the solvent is an organic solvent.

[10]

The liquid container as described in [9] contains an organic solvent selected from at least one selected from the group consisting of 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, cyclobutanone, cycloheptanone and 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, amyl propionate, isoamyl propionate, ethylcyclohexane, mesitylene and decane.

[11]

The drug solution container as described in any of [1] to [10], wherein the number of metal nanoparticles with a particle size of 0.5 to 17 nm in each unit volume of the drug solution is 1.0 × ^10¹ to 1.0 × ^10⁹ particles/ ^cm³ .

[12]

The liquid container as described in any one of [1] to [11], wherein the gas comprises nitrogen, the nitrogen content is 95 to 99.9999% of the total volume of the voids, and the content of the organic compound in the gas is 0.05 to 50,000 ppt of the total mass of the liquid.

[13]

The liquid medicine container as described in any of [1] to [12], wherein the porosity of the container in the liquid medicine container is 50 to 99.99% by volume.

[14]

The liquid container as described in any of [1] to [13], wherein at least a portion of the liquid-receiving portion of the container is made of fluororesin, electrolytically polished stainless steel, or glass.

[15]

As described in [14], in the case where at least a portion of the liquid-receiving portion of the container is made of the electrolytically polished stainless steel, the average surface roughness Ra of the liquid-receiving portion of the container is less than 100 nm.

[16]

As described in [14], at least a portion of the liquid-receiving portion of the container, together with the fluororesin, also comprises a conductive material.

[17]

The liquid container as described in [16] contains carbon as the conductive material.

[18]

As described in [17], the carbon is selected from at least one of the group consisting of carbon particles, carbon nanotubes, and carbon fillers.

[19]

The liquid container as described in any one of [1] to [18], wherein the liquid is used as a raw material selected from at least one liquid selected from the group consisting of developer, washing solution, wafer cleaning solution, wire cleaning solution, pre-wetting solution, photoresist, lower film forming solution, upper film forming solution, and hard coating forming solution.

As shown below, according to the present invention, a drug container with excellent defect suppression performance can be provided for a drug solution.

The present invention will now be described.

The following description of the constituent elements is sometimes based on representative embodiments of the invention, but the invention is not limited to those embodiments.

Furthermore, in this manual, the range of values represented by "~" refers to the range encompassed by the values before and after "~" as the lower and upper limits.

Furthermore, in this invention, "ppm" refers to "parts-per-million ( ^10⁻⁶ )", "ppb" refers to "parts-per-billion ( ^10⁻⁹ )", "ppt" refers to "parts-per-trillion ( ^10⁻¹² )", and "ppq" refers to "parts-per-quadrillion ( ^10⁻¹⁵ )".

Furthermore, in the designation of group (atomic group) in this invention, the absence of markings indicating whether it is substituted or unsubstituted, to the extent that it does not impair the effect of this invention, includes not only those without substituents but also those with substituents. For example, the term "alkali" includes not only unsubstituted alkalis (unsubstituted alkalis) but also substituted alkalis (substituted alkalis). This applies to all compounds as well.

Furthermore, "radiation" in this invention refers to, for example, far-ultraviolet radiation, extreme ultraviolet radiation (EUV), X-rays, or electron beams. Also, "light" in this invention refers to photochemical radiation or radiation. Unless otherwise stated, "exposure" in this invention includes not only exposure using far-ultraviolet radiation, X-rays, or EUV, but also depiction using particle beams such as electron beams or ion beams.

[Drug Liquid Containment Container]

The liquid medicine container of this invention (hereinafter also referred to as "this liquid medicine container") is a liquid medicine container having a container and a liquid medicine contained within the container.

Furthermore, within this drug solution container, the aforementioned drug solution contains a solvent, metal-containing particles containing metal atoms, and an organic compound with a ClogP value higher than that of the solvent (hereinafter also referred to as "specific organic compound A").

Furthermore, in this pharmaceutical solution container, the content of particles containing the aforementioned metals is less than 10 ppt relative to the total mass of the pharmaceutical solution.

Furthermore, in this pharmaceutical solution container, a gas containing an organic compound (hereinafter also referred to as "specific organic compound B") with a ClogP value higher than that of the solvent is present in the pores of the container, and the total content of the specific organic compound A and the specific organic compound B is less than 100,000 ppt relative to the total mass of the pharmaceutical solution.

While the mechanism by which this liquid containment device solves the aforementioned problems may not be entirely clear, the inventors hypothesize the following mechanism. Furthermore, this mechanism is hypothetical, and even if the effects of this invention are achieved through different mechanisms, they are still included within the scope of this invention.

Organic compounds and metal particles contained in the solution can themselves be causes of defects, but their aggregation easily forms complex particles that contribute to defect formation. In particular, the presence of organic compounds with a ClogP value higher than that of the solvent (specific organic compounds) easily leads to the formation of complex particles combining these specific organic compounds and metal particles, thus making defect formation more significant.

As a solution to this problem, methods to reduce the content of specific organic compounds in the drug solution could be considered. However, sometimes this method cannot adequately suppress the generation of defects.

The reason is believed to be that certain organic compounds contained in the gas within the container's pores can mix into the liquid during transport and storage. In other words, sometimes the content of these specific organic compounds increases when the liquid is contained in a container compared to immediately after manufacturing (before being contained), thus making the defect more pronounced.

It is presumed that the total content of specific organic compound A and specific organic compound B in this drug solution container falls within the aforementioned range, thus resulting in a drug solution container with excellent containment defect suppression performance.

[Medicinal Solution]

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

Solvents

The solution contains a solvent. At least one of water and organic solvents can be cited as solvents, with organic solvents being preferred.

Furthermore, in this instruction manual, the term "organic solvent" refers to the liquid organic compound present in a concentration exceeding 10,000 ppm (parts by mass) of each component relative to the total mass of the drug solution. In other words, in this instruction manual, liquid organic compounds present in a concentration exceeding 10,000 ppm (parts by mass) relative to the total mass of the drug solution are considered organic solvents.

Furthermore, in this instruction manual, the term "liquid" refers to a liquid state at 25°C and atmospheric pressure.

There are no particular restrictions on the type of organic solvent used; any known organic solvent can be used. Examples of organic solvents include, for instance, alkyl glycol monoalkyl ether carboxylic esters, alkyl glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionate esters, cyclic lactones (preferably with 4 to 10 carbon atoms), monoketone compounds that may have a ring (preferably with 4 to 10 carbon atoms), alkyl carbonates, alkyl alkoxyacetic acids, and alkyl pyruvate esters.

Furthermore, as an organic solvent, for example, those described in Japanese Patent Application Publication Nos. 2016-057614, 2014-219664, 2016-138219, and 2015-135379 may be used.

As organic solvents, those selected include 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, diisopentanone, butyl acetate (nBA), isoamyl acetate (iAA), isopropanol, and 4-methyl-2-pentanol (M At least one of the following groups is preferred: IBC, dimethyl sulfoxide, N-methyl-2-pyrrolidone (NMP), diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, propylene carbonate (PC), cyclobutane, cycloheptanone, 1-hexanol, decane, 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, isoamyl propionate, ethylcyclohexane, and mesitylene.

Among these, considering superior defect suppression performance, at least one ingredient selected from the group consisting of CHN, nBA, NMP, EL, PGMEA, PGME, PC, iAA, propylene glycol monomethyl ether, propylene glycol monopropyl ether, methyl methoxypropionate, cyclopentanone, γ-butyrolactone, diisopentanone, isopropanol, dimethyl sulfoxide, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, cyclobutanone, cycloheptanone, 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, isopentyl propionate, ethylcyclohexane, mesitylene, and decane is preferred.

There are no particular restrictions on the content of organic solvents in the solution, but generally, relative to the total mass of the solution, 98.0% by mass or higher is preferred, 99.0% by mass or higher is even better, 99.9% by mass or higher is further preferred, and 99.99% by mass or higher is exceptionally preferred. There is no particular upper limit, but it is usually less than 100% by mass.

Organic solvents can be used alone or in combination with two or more. When using two or more organic solvents, it is preferable that the total content be within the above-mentioned range.

In addition, the type and content of organic solvents in the drug solution can be measured using gas chromatography-mass spectrometry.

<Metal-containing particles>

The liquid contains metal particles that contain metal atoms.

The following describes a preferred form of the method for manufacturing a pharmaceutical solution; however, pharmaceutical solutions are generally manufactured by purifying a substance containing a pre-described solvent and organic compounds. Metal particles can be added to the pharmaceutical solution manufacturing process, depending on the intended use; they can also be directly contained in the substance being purified, or they can migrate from the pharmaceutical solution manufacturing apparatus during the manufacturing process (so-called contamination).

There are no particular restrictions on the metal atoms used, but examples include Fe, Al, Cr, Ni, Pb, Zn, and Ti atoms. Among these, strictly controlling the content of metal-containing particles (Fe, Al, Pb, Zn, and Ti) in the solution can easily yield superior defect suppression performance. Furthermore, strictly controlling the content of Pb and Ti-containing particles in the solution can easily lead to even better defect suppression performance.

That is, as a metal atom, it is preferable to select at least one from the group including Fe, Al, Cr, Ni, Pb, Zn, and Ti atoms; more preferably, it is preferable to select at least one from the group including Fe, Al, Pb, Zn, and Ti atoms; even more preferably, it is preferable to select at least one from the group including Pb and Ti atoms; and it is especially preferable that the metal-containing particle contains either Pb or Ti atoms.

Furthermore, metal-containing particles may contain only one of the aforementioned metal atoms, or they may contain two or more of them.

While there are no particular restrictions on the particle size of metal-containing particles, the content of particles with a size of approximately 0.1 to 100 nm is often a controlled factor, for example, in semiconductor device manufacturing solutions.

As is known from the inventors' research, particularly in the photoresist manufacturing process using EUV (Extreme Ultraviolet) exposure, by controlling the content of metal-containing particles (hereinafter also referred to as "metal nanoparticles") with a particle size of 0.5~17nm in the solution, it is easy to obtain a solution with excellent defect suppression performance. In EUV photoresist manufacturing processes, fine resist spacing, resist width, and resist gaps are often required. In such cases, it is necessary to control the number of even finer particles, which do not cause any problems in conventional processes.

There are no particular limitations on the particle size distribution used as a criterion for the number of metal-containing particles. However, from the viewpoint of obtaining a drug solution with superior effects of the present invention, it is preferable that at least one of the groups selected, including those with particle sizes less than 5 nm and those with particle sizes greater than 17 nm, has an extreme value.

In other words, it is preferable that there are no maximum values in the particle size range of 5-17 nm. By ensuring that there are no maximum values in the particle size range of 5-17 nm, the solution exhibits superior defect suppression performance, especially superior bridging defect suppression performance. Bridging defects refer to poor interconnections between wiring patterns.

Furthermore, considering the need for a solution exhibiting superior effects compared to this invention, it is particularly desirable to have an extremely large particle size distribution in the range of 0.5 nm or larger and smaller than 5 nm. Through the above, the solution demonstrates superior bridging defect suppression performance.

The content of metal particles relative to the total mass of the drug solution should be less than 10 ppt, with 0.001 to 10 ppt being preferred.

If the content of metal particles is less than 10 ppt by mass, defects caused by metal particle aggregation can be suppressed. If the content of metal particles is 0.01 ppt by mass or more, although the exact reason is unclear, the interaction between the metal particles and the wiring substrate is reduced, making it difficult for the metal particles to remain on the substrate, thus suppressing defects.

To maximize the aforementioned effects, the upper limit for the content of metal particles is preferably below 5 ppt (mass weight), preferably below 1 ppt (mass weight), and ideally below 0.1 ppt (mass weight).

To maximize the aforementioned effects, a minimum metal particle content of 0.001 ppt is preferred, and 0.01 ppt is exceptionally preferred.

The types and amounts of metal-containing particles can be measured using SP-ICP-MS (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry).

The SP-ICP-MS method used here employs the same apparatus as the conventional ICP-MS (Inductively Coupled Plasma Mass Spectrometry) method, differing only in data analysis. Data analysis for the SP-ICP-MS method can be performed using commercially available software.

In ICP-MS, the content of the metal component being measured is independent of its form of existence. Furthermore, the metal component refers to metal ions and metal-containing particles. Therefore, the total mass of the metal-containing particles and metal ions being measured is determined as the content of the metal component.

On the other hand, SP-ICP-MS can measure the content of metal-containing particles. Therefore, by subtracting the content of metal-containing particles from the content of metal components in the sample, the content of metal ions in the sample can be calculated.

As for devices for SP-ICP-MS, for example, the Agilent Technologies Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200) can be used to perform measurements by the method described in the embodiments. Other devices besides the above, in addition to the PerkinElmer Co., Ltd. NexION 350S, can also be used, such as the Agilent 8900 manufactured by Agilent Technologies.

(Metal nanoparticles)

Metal nanoparticles refer to metal-containing particles with a particle size of 0.5–17 nm.

The number of metal nanoparticles per unit volume of the drug solution is preferably 1.0× ^10⁰ to 1.0× ^10⁹ particles/ ^cm³ . Considering the superior efficacy of the present invention, a particle count of 1.0× ^10¹ particles/ ^cm³ or higher is preferred, 1.0× ^10⁷ particles/ ^cm³ or lower is preferred, and 1.0× ^10⁵ particles/ ^cm³ or lower is even better.

If the number of metal nanoparticles in each unit volume of the drug solution is 1.0× ^10¹ ~ 1.0× ^10⁹ particles/ ^cm³ , then the drug solution has superior defect suppression performance.

Furthermore, the content of metal nanoparticles in the drug solution can be measured using the method described in the embodiments. The number of metal nanoparticles per unit volume of drug solution is calculated by rounding to two significant figures.

There are no particular limitations on the metal atoms contained in the metal nanoparticles, but they are the same as those already described in the description of metal atoms contained in metal-containing particles. From the viewpoint of obtaining a liquid with superior effects of the present invention, it is preferable that the metal atoms be selected from at least one of the group including Pb atoms and Ti atoms, and it is even more preferable that the metal nanoparticles contain both Pb atoms and Ti atoms. The phrase "metal nanoparticles containing both Pb atoms and Ti atoms" typically refers to a liquid containing both Pb-containing metal nanoparticles and Ti-containing metal nanoparticles.

Furthermore, there is no particular limitation on the ratio (Pb/Ti) of the number of Pb-containing metal nanoparticles (hereinafter also referred to as "Pb nanoparticles") and Ti-containing metal nanoparticles (hereinafter also referred to as "Ti nanoparticles") in the solution, but it is generally preferred to be 1.0× ^10⁻⁴ to 3.0, more preferred to be 1.0× ^10⁻³ to 2.0, and particularly preferred to be 1.0× ^10⁻² to 1.5. If the Pb/Ti ratio is 1.0× ^10⁻³ to 2.0, the solution exhibits superior effects of the present invention, especially superior bridging defect suppression performance.

The inventors have discovered that Pb nanoparticles and Ti nanoparticles are prone to bonding when applied to a wafer, for example, and are easily developed into defects (especially bridging defects) during photoresist film development.

If Pb/Ti is 1.0 × ^10⁻³ ~ 2.0, it is surprisingly easier to suppress the generation of defects. In addition, in this specification, Pb/Ti and A/(B+C) mentioned later are rounded to two significant digits.

Metal nanoparticles can contain metal atoms, and their morphology is not particularly limited. Examples include monomers of metal atoms, compounds containing metal atoms (hereinafter also referred to as "metal compounds"), and composites of these. Furthermore, metal nanoparticles can contain a plurality of metal atoms. In the case of metal nanoparticles containing a plurality of metals, the metal atom with the highest abundance (atm%) among these plurality of metals is taken as the principal component. Therefore, when called Pb nanoparticles, in the case of containing a plurality of metals, Pb atoms are the principal component among the plurality of metals.

There are no particular limitations on what constitutes a composite, but examples include so-called core-shell particles of monomers containing metal atoms and metal compounds covering at least a portion of the aforementioned monomers of metal atoms; solid solution particles containing metal atoms and other atoms; eutectic particles containing metal atoms and other atoms; aggregate particles of monomers of metal atoms and metal compounds; aggregate particles of different types of metal compounds; and metal compounds whose composition changes continuously or intermittently from the particle surface toward the center.

There are no particular restrictions on the atoms other than the metal atoms contained in the metallic compound, but examples include carbon, oxygen, nitrogen, hydrogen, sulfur, and phosphorus atoms, with oxygen atoms being preferred. There are no particular restrictions on the form in which the oxygen atom is contained in the metallic compound, but oxides of the metal atom are preferred.

From the viewpoint of obtaining a medicinal solution with superior effects of the present invention, the metal nanoparticles are preferably selected from at least one of the following groups: particles composed of monomers of metal atoms (particle A), particles composed of oxides of metal atoms (particle B), and particles composed of monomers of metal atoms and oxides of metal atoms (particle C).

Furthermore, there are no particular limitations on the relationship between the number of particles A, B, and C in the number of metal nanoparticles per unit volume of the drug solution. However, from the viewpoint of obtaining a drug solution with superior effects of the present invention, it is preferable that the ratio of the number of particles A to the total number of particles B and C (hereinafter also referred to as "A/(B+C)") is 1.5 or less, less than 1.0 is more preferable, less than 2.0 × ^10⁻¹ is further preferable, less than 1.0 × ^10⁻¹ is particularly preferable, more than 1.0 × ^10⁻³ is preferable, and more than 1.0 × ^10⁻² is more preferable.

If A/(B+C) is less than 1.0, the solution exhibits superior bridging defect suppression performance, superior pattern width uniformity, and superior stain defect suppression performance. Furthermore, stain defects refer to defects where no metal atoms were detected.

Furthermore, if A/(B+C) is less than 0.1, the drug solution exhibits superior defect inhibition performance.

<Specific organic compound A>

The drug solution contains a specific organic compound A. As mentioned above, specific organic compound A is an organic compound in the drug solution whose ClogP value is higher than that of the solvent.

A specific organic compound A may be added to the drug solution, or it may be unintentionally mixed into the drug solution during the manufacturing process. Examples of unintentional mixing during the manufacturing process include the presence of specific organic compound A in the raw materials used in the manufacturing process (e.g., organic solvents), and the mixing (e.g., contamination) of water during the manufacturing process, but are not limited to the above.

The ClogP value of a specific organic compound A is higher than the ClogP value of the solvent in the drug solution. From the perspective of further enhancing the effectiveness of this invention, the difference between the ClogP value of the specific organic compound A and the ClogP value of the solvent in the drug solution [(ClogP value of specific organic compound A) - (ClogP value of solvent in drug solution)] is preferably 3-9, 3-8 is preferred, and 4-7 is even better.

There are no particular limitations as long as the ClogP value of a specific organic compound A is higher than the ClogP value of the solvent in the drug solution. However, from the perspective of maximizing the effectiveness of this invention, a value of 6 or higher is preferred, and 6 to 10 is particularly preferred.

The ClogP value refers to the value obtained by calculating the common logarithm logP of the partition coefficient P of 1-octanol and water. While known methods and software can be used for calculating the ClogP value, this invention uses the ClogP program incorporated into Cambridge Soft's ChemBioDraw Ultra 12.0 unless otherwise specified.

For example, dibutyl phthalate has a ClogP value of 4.72, dioctyl phthalate (DOP) has a ClogP value of 8.71, and diisononyl phthalate (DINP) has a ClogP value of 9.03.

There is no particular limitation on the number of carbons in the specific organic compound A. However, considering the superior efficacy of the invention, 8 or more carbons are preferred, and 12 or more are even better. Furthermore, there is no particular upper limit on the number of carbons, but generally, 30 or less is preferred.

As a specific organic compound A, it may be a byproduct and/or unreacted starting material generated during the synthesis of an organic solvent (hereinafter also referred to as "byproducts, etc.").

Examples of the aforementioned byproducts include compounds represented by formulas I to V.

In Formula I, _R1 and _R2 independently represent alkyl or cycloalkyl groups or rings formed by bonding with each other.

As for the alkyl or cycloalkyl groups represented by _R1 and _R2 , alkyl groups having 1 to 12 carbon atoms or cycloalkyl groups having 6 to 12 carbon atoms are preferred, and alkyl groups having 1 to 8 carbon atoms or cycloalkyl groups having 6 to 8 carbon atoms are even more preferred.

The ring formed by the bonding of _R1 and _R2 is a lactone ring. A lactone ring with 4 to 9 members is preferred, and a lactone ring with 4 to 6 members is even better.

In addition, it is preferable that _R1 and _R2 satisfy the relationship that the number of carbon atoms in the compound represented by Formula I is 8 or more.

In Formula II, _R3 and _R4 independently represent hydrogen atoms, alkyl groups, alkenyl groups, cycloalkyl groups, or cycloalkenyl groups, or are bonded together to form a ring. However, _R3 and _R4 are not both hydrogen atoms.

Alkyl groups represented by _R3 and _R4 are preferred, for example, alkyl groups having 1 to 12 carbon atoms are preferred, and alkyl groups having 1 to 8 carbon atoms are even more preferred.

Alkenes represented by _R3 and _R4 are preferred, for example, alkenes with 2 to 12 carbons are preferred, and alkenes with 2 to 8 carbons are even more preferred.

As cycloalkyl groups represented by _R3 and _R4 , cycloalkyl groups with 6 to 12 carbon atoms are preferred, and cycloalkyl groups with 6 to 8 carbon atoms are even more preferred.

Cycloalkenyl groups represented by _R3 and _R4 are preferred, for example, cycloalkenyl groups with 3 to 12 carbon atoms are preferred, and cycloalkenyl groups with 6 to 8 carbon atoms are even more preferred.

The ring formed by the bonding of _R3 and _R4 is a cyclic ketone structure, which can be a saturated cyclic ketone or an unsaturated cyclic ketone. It is preferred that the cyclic ketone has 6 to 10 members, and even more preferred that it has 6 to 8 members.

In addition, it is preferable that _R3 and _R4 satisfy the relationship that the number of carbon atoms in the compound represented by Formula II is 8 or more.

In Formula III, _R5 represents alkyl or cycloalkyl.

The alkyl group represented by R ₅ is preferably an alkyl group with 6 or more carbon atoms, more preferably an alkyl group with 6 to 12 carbon atoms, and especially preferably an alkyl group with 6 to 10 carbon atoms.

The aforementioned alkyl groups may have ether bonds in the chain, or they may have substituents such as hydroxyl groups.

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

In Formula IV, _R6 and _R7 independently represent alkyl or cycloalkyl groups or rings formed by bonding with each other.

As for alkyl groups represented by _R6 and _R7 , alkyl groups with 1 to 12 carbon atoms are preferred, and alkyl groups with 1 to 8 carbon atoms are even more preferred.

As cycloalkyl groups represented by _R6 and _R7 , cycloalkyl groups with 6 to 12 carbon atoms are preferred, and cycloalkyl groups with 6 to 8 carbon atoms are even more preferred.

The ring formed by the bonding of _R6 and _R7 is a cyclic ether structure. The cyclic ether structure is preferably 4 to 8 members, and even more preferably 5 to 7 members.

In addition, it is preferable that _R6 and _R7 satisfy the relationship that the compound represented by Formula IV has 8 or more carbon atoms.

In formula V, _R8 and _R9 independently represent alkyl or cycloalkyl groups or rings formed by bonding with each other. L represents a single bond or an extended alkyl group.

Alkyl groups represented by _R8 and _R9 are preferred, for example, alkyl groups with 6 to 12 carbon atoms are preferred, and alkyl groups with 6 to 10 carbon atoms are even more preferred.

As for cycloalkyl groups represented by _R8 and _R9 , cycloalkyl groups with 6 to 12 carbon atoms are preferred, and cycloalkyl groups with 6 to 10 carbon atoms are even more preferred.

The ring formed by the bonding of _R8 and _R9 is a cyclic diketone structure. The cyclic diketone structure with 6 to 12 members is preferred, and with 6 to 10 members is even more preferred.

As for the alkyl group represented by L, alkyl groups with 1 to 12 carbon atoms are preferred, and alkyl groups with 1 to 10 carbon atoms are even more preferred.

In addition, _R8 , _R9 and L satisfy the relationship that the number of carbon atoms in the compound represented by formula V is 8 or more.

There are no particular restrictions, but when the organic solvent is a amide compound, amide compound, or monoxide compound, examples can be given of amide compounds, amide compounds, and monoxide compounds having 6 or more carbon atoms in their form. Furthermore, as a specific organic compound A, the following compounds can also be given as examples.

Furthermore, examples of specific organic compounds A include dibutylhydroxytoluene (BHT), distearate (DSTP), 4,4'-endylenyl bis-(6-tert-butyl-3-methylphenol), 2,2'-methylene bis-(4-ethyl-6-tert-butylphenol), and antioxidants as described in Japanese Patent Application Publication No. 2015-200775; unreacted raw materials; structural isomers and byproducts generated during the manufacture of organic solvents; leachates from components of the apparatus constituting the organic solvent (e.g., plasticizers leached from rubber components such as O-rings); etc.

Furthermore, as specific organic compounds A, examples include dioctyl phthalate (DOP), bis(2-ethylhexyl) phthalate (DEHP), bis(2-propylheptaethyl) phthalate (DPHP), dibutyl phthalate (DBP), benzyl butyl phthalate (BBzP), diisodecyl phthalate (DIDP), diisooctyl phthalate (DIOP), diethyl phthalate (DEP), diisobutyl phthalate (DIBP), dihexyl phthalate, and diisononyl phthalate (DINP), as well as tri(2-ethyl) trimellitate. Hexyl ester (TEHTM), tri(n-octyl-n-decyl) trimellitate (ATM), bis(2-ethylhexyl) adipate (DEHA), monomethyl adipate (MMAD), dioctyl adipate (DOA), dibutyl sebacate (DBS), dibutyl bis(butenedioic acid) (DBM), diisobutyl bis(butenedioic acid) (DIBM), azelaate, benzoate, ethylene terephthalate (e.g., dioctyl terephthalate (DEHT)), diisononyl 1,2-cyclohexanedicarboxylate (DINCH), epoxidized vegetable oils, sulfonamides (e.g., N-(2-hydroxypropyl)benzenesulfonamide (HP)). BSA), N-(n-butylbenzenesulfonamide) (BBSA-NBBS), organophosphates (e.g., tricresyl phosphate (TCP), tributyl phosphate (TBP)), acetylated glycerol monoesters, triethyl citrate (TEC), triethyl acetylated citrate (ATEC), tributyl citrate (TBC), tributyl acetylated citrate (ATBC), trioctyl citrate (TOC), trioctyl acetylated citrate (ATOC), trihexane citrate (THC), trihexane citrate (ATHC), epoxidized soybean oil, ethylenepropyl rubber, polybutene, addition polymers of 5-ethylene-2-norbornene, and the following polymeric plasticizers.

It is presumed that specific organic compounds A were introduced into the purified substance or solution through filters, piping, tanks, O-rings, and containers encountered during the purification process. In particular, compounds other than alkylene compounds are associated with the generation of bridging defects.

Among the aforementioned compounds, phthalates are preferred because specific organic compound A is typically present in the pharmaceutical solution manufacturing environment and its content can be easily adjusted through manufacturing steps and methods. It is particularly preferred that at least one compound be selected from the group consisting of dioctyl phthalate (DOP) and diisononyl phthalate (DINP).

There are no particular limitations as long as the total content of specific organic compound A and the content of organic compounds (organic compound B, described later) contained in the gas present in the pores are within the range described later. However, considering superior defect suppression performance, a total mass of less than 100,000 ppt of the solution is preferred, 0.1 to 1,000 ppt is more preferred, and 0.1 to 10 ppt is particularly preferred.

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

Other ingredients

The solution may contain other ingredients besides those mentioned above. Examples of other ingredients include organic compounds other than specific organic compound A, and resins, etc.

(Organic compounds other than specific organic compound A)

The solution may contain organic compounds other than specific organic compound A (hereinafter also referred to as "other organic compounds"). Other organic compounds are organic compounds whose ClogP value is lower than the ClogP value of the solvent in the solution.

Other organic compounds may be added to the drug solution, or they may be unintentionally mixed into the drug solution manufacturing process. Examples of unintentional mixing during the drug solution manufacturing process include the presence of other specific organic compounds in the raw materials used in the manufacturing process (e.g., organic solvents), and the mixing (e.g., contamination) of water during the drug solution manufacturing process, but are not limited to the above.

(resin)

The solution may contain resin. Resin P, having groups that decompose under acidic conditions to produce polar groups, is preferred. Of the aforementioned resins, those that reduce the solubility of developing solutions primarily composed of organic solvents under acidic conditions, i.e., resins having repeating units represented by the formula (AI) described later, are preferred. Resins having repeating units represented by the formula (AI) described later have groups that decompose under acidic conditions to produce alkaline-soluble groups (hereinafter also referred to as "acid-decomposing groups").

Examples of polar groups include alkali-soluble groups. Examples of alkali-soluble groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), phenolic hydroxyl groups, and sulfonyl groups.

In acid-dissociative groups, the polar group is protected by a group that is released under the action of acid (acid-dissociative group). Examples of acid-dissociative groups 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 independently represent alkyl, cycloalkyl, aryl, aralkyl, or alkenyl groups. R ₃₆ and R ₃₇ can bond together to form a ring.

R ₀₁ and R ₀₂ represent hydrogen atoms, alkyl, cycloalkyl, aryl, aralkyl or alkenyl groups, respectively.

The following section details resin P, which reduces the solubility of developer solutions primarily composed of organic solvents through the action of acids.

((Equation (AI): A repeating unit with an acid-decomposing group))

Resin P containing repeating units represented by formula (AI) is preferred.

[Chemical Formula 5]

In formula (AI), Xa ₁ represents a hydrogen atom or an alkyl group that may have substituents.

T represents a single-bond or divalent linker.

Ra ₁ to Ra ₃ represent alkyl (straight-chain or branched) or cycloalkyl (monocyclic or polycyclic) independently.

Two of Ra ₁ to Ra ₃ can bond together to form a cycloalkyl group (monocyclic or polycyclic).

As an alkyl group represented by Xa _1, which can have substituents, examples include methyl and groups represented by -CH ₂ -R _{11. R 11} represents a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organic group.

Xa ₁ is preferably a hydrogen atom, methyl, trifluoromethyl or hydroxymethyl.

Examples of divalent linking groups to T include alkylene groups, -COO-Rt- groups, and -O-Rt- groups. In these formulas, Rt represents an alkylene group or a cycloalkylene group.

T is preferably a single bond or a -COO-Rt- group. Rt is preferably an alkyl group with 1 to 5 carbon atoms, and _-CH2- , -( _CH2 ) _2- , or -( _CH2 ) _3- are even better.

For alkyl groups of Ra ₁ to Ra ₃ , 1 to 4 carbon atoms are preferred.

As cycloalkyl groups of Ra ₁ to Ra ₃ , monocyclic cycloalkyl groups such as cyclopentyl or cyclohexyl, or polycyclic cycloalkyl groups such as norcenyl, tetracyclodecyl, tetracyclododecyl, or adamantyl are preferred.

As a cycloalkyl group formed by bonding two Ra ₁ to Ra ₃ atoms, monocyclic cycloalkyl groups such as cyclopentyl or cyclohexyl, or polycyclic cycloalkyl groups such as norcenyl, tetracyclodecyl, tetracyclododecyl, or adamantyl are preferred. Monocyclic cycloalkyl groups with 5 to 6 carbon atoms are even more preferred.

In the above-mentioned cycloalkyl groups formed by bonding two Ra ₁ to Ra ₃ , for example, one of the methylene groups constituting the ring can be replaced by a group having heteroatoms such as an oxygen atom or a carbonyl group.

In the repeating unit represented by formula (AI), it is preferable that Ra ₁ is methyl or ethyl and Ra ₂ and Ra ₃ are bonded to form the above-mentioned cycloalkyl group.

The aforementioned groups may have substituents. Examples of substituents include alkyl groups (1-4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1-4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2-6 carbon atoms), with 8 or fewer carbon atoms being preferred.

The content of repeating units, expressed by formula (AI), relative to the total repeating units in resin P is preferably 20-90 mol%, more preferably 25-85 mol%, and particularly preferably 30-80 mol%.

((Repeating units with lactone structures))

Furthermore, resin P containing a repeating unit Q with a lactone structure is preferred.

The repeating unit Q, having a lactone structure, is preferably derived from a (meth)acrylic acid derivative monomer, and even more preferably.

The repeating unit Q with a lactone structure can be used alone or in combination with two or more types, but using one type alone is preferred.

The content of repeating units Q with lactone structures relative to the total repeating units in resin P is preferably 3-80 mol%, and more preferably 3-60 mol%.

As a lactone structure, a 5-7 membered lactone structure is preferred, and structures that form bicyclic or spirocyclic structures with other ring structures are even more preferred.

As a lactone structure, it is preferable to contain a repeating unit having any one of the lactone structures represented by formulas (LC1-1) to (LC1-17). As a lactone structure, a lactone structure represented by formula (LC1-1), formula (LC1-4), formula (LC1-5), or formula (LC1-8) is preferred, and a lactone structure represented by formula (LC1-4) is even more preferred.

The lactone structure may have substituents (Rb ₂ ). Preferred substituents (Rb ₂ ) include alkyl groups with 1-8 carbon atoms, cycloalkyl groups with 4-7 carbon atoms, alkoxy groups with 1-8 carbon atoms, alkoxycarbonyl groups with 2-8 carbon atoms, carboxyl groups, halogen atoms, hydroxyl groups, cyano groups, and acid-degradable groups. n ₂ represents an integer from 0 to 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 bond together to form a ring.

((a repeating unit containing a phenolic hydroxyl group))

Furthermore, resin P can contain repeating units with phenolic hydroxyl groups.

As a repeating unit containing a phenolic hydroxyl group, an example of a repeating unit represented by the following general formula (I) can be cited.

In the formula, R ₄₁ , R ₄₂ , and R ₄₃ independently represent a hydrogen atom, an alkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R ₄₂ can bond with Ar ₄ to form a ring, in which case R ₄₂ represents a single bond or an extended alkyl group.

X ₄ indicates a single bond, -COO- or -CONR _64- , and R ₆₄ indicates a hydrogen atom or alkyl group.

_L4 indicates a single bond or an alkyl group.

Ar ₄ represents an aromatic cyclic group with an (n+1) valence. When it is bonded to R ₄₂ to form a ring, it represents an aromatic cyclic group with an (n+2) valence.

n represents an integer from 1 to 5.

The alkyl groups R ₄₁ , R ₄₂ and R ₄₃ in general formula (I) may have substituents. Alkyl groups with 20 or fewer carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, dibutyl, hexyl, 2-ethylhexyl, octyl and dodecyl, are preferred. Alkyl groups with 8 or fewer carbon atoms are even more preferred. Alkyl groups with 3 or fewer carbon atoms are particularly preferred.

The cycloalkyl groups R ₄₁ , R ₄₂ , and R ₄₃ in general formula (I) can be monocyclic or polycyclic. As cycloalkyl groups, they can have substituents, and monocyclic cycloalkyl groups with 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, and cyclohexyl, are preferred.

As for the halogen atoms R ₄₁ , R ₄₂ and R ₄₃ in general formula (I), fluorine, chlorine, bromine and iodine atoms can be mentioned, with fluorine atoms being preferred.

The alkyl group contained in the alkoxycarbonyl group of _R41 , _R42 and _R43 in general formula (I) is preferably the same as the alkyl group in _R41 , _R42 and _R43 mentioned above.

Examples of substituents among the aforementioned groups include alkyl, cycloalkyl, aryl, amino, amide, urea, carbamate, hydroxyl, carboxyl, halogen, alkoxy, thioether, acetyl, acetoxy, alkoxycarbonyl, cyano, and nitro groups. It is preferable that the substituent has 8 or fewer carbon atoms.

Ar ₄ represents an aromatic cyclic group with an (n+1) valence. A divalent aromatic cyclic group with n=1 can have substituents, such as arylyl groups with 6-18 carbon atoms (e.g., phenyl, methylaryl, naphthyl, and anthracene), as well as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, and triphenyl ether. Aromatic cyclic groups containing heterocyclic compounds, such as imidazole, benzimidazole, triazole, thiadiazole, and thiazolium.

As a specific example of an aromatic cycloalcoholic group with a valence of (n+1) when n is an integer greater than 2, a group formed by removing (n-1) any hydrogen atoms from the above-mentioned specific example of a divalent aromatic cycloalcoholic group can be given.

(n+1) valence aromatic cyclic groups can also have substituents.

As substituents capable of having the above-mentioned alkyl, cycloalkyl, alkoxycarbonyl, alkylene, and (n+1) valence aromatic cyclic groups, examples include alkyl groups listed in R ₄₁ , R ₄₂ , and R ₄₃ of general formula (I); alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; and aryl groups such as phenyl.

As the alkyl group of R ₆₄ in -CONR _64- (where R ₆₄ represents a hydrogen atom or alkyl group) represented by X ₄ , it may have substituents, such as methyl, ethyl, propyl, isopropyl, n-butyl, dibutyl, hexyl, 2-ethylhexyl, octyl and dodecyl, which have 20 or fewer carbon atoms, and alkyl groups with 8 or fewer carbon atoms are preferred.

For _X4 , single key, -COO-, or -CONH- are preferred, with single key or -COO- being even better.

As for the alkyl group in _L4 , it can have substituents, and alkyl groups with 1 to 8 carbons such as methylene, ethyl, propyl, butyl, hexyl and octyl are preferred.

As for Ar ₄ , it is preferable to have an aromatic cyclic group with 6 to 18 carbon atoms as the substituent, and phenyl cyclic, naphthyl cyclic or biphenyl cyclic are even more preferred.

It is preferable that the repeating unit represented by general formula (I) has a hydroxystyrene structure. That is, it is preferable that Ar ₄ is a phenylcyclohexyl group.

The content of repeating units containing phenolic hydroxyl groups relative to the total repeating units in resin P is preferably 0-50 mol%, more preferably 0-45 mol%, and exceptionally preferably 0-40 mol%.

((Repeating units containing organic groups with polar radicals))

Resin P may contain repeating units that include organic groups with polar radicals; more particularly, it may contain repeating units that have an alicyclic hydrocarbon structure substituted with polar radicals. This improves substrate adhesion and developer affinity.

For alicyclic hydrocarbon structures substituted with polar groups, diamond-alkyl, diamond-alkyl, or norberargyl groups are preferred. Hydroxyl or cyano groups are preferred as polar groups.

When resin P contains repeating units, the content of these repeating units relative to the total repeating units in resin P is preferably 1-50 mol%, more preferably 1-30 mol%, further preferably 5-25 mol%, and especially preferably 5-20 mol%, wherein the repeating unit contains an organic group having a polar group.

(Repeating units represented by general formula (VI))

Resin P may contain repeating units represented by the following general formula (VI).

In general formula (VI), R ₆₁ , R ₆₂ , and R ₆₃ independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R ₆₂ can bond with Ar ₆ to form a ring, in which case R ₆₂ represents a single bond or an extended alkyl group.

X ₆ indicates a single bond, -COO-, or -CONR _64- . _{R 64} indicates a hydrogen atom or an alkyl group.

_L6 indicates a single bond or an alkyl group.

Ar ₆ represents an aromatic cyclic group with an (n+1) valence. When it is bonded to R ₆₂ to form a ring, it represents an aromatic cyclic group with an (n+2) valence.

When _Y2 is n≧2, it independently represents either a hydrogen atom or a group that is removed by the action of an acid. However, at least one of _Y2 represents a group that is removed by the action of an acid.

n represents an integer from 1 to 4.

The structure represented by the following general formula (VI-A) is preferred for _Y2 as a group that is desorbed by the action of acid.

_L1 and _L2 represent hydrogen atoms, alkyl, cycloalkyl, aryl, or a combination of alkyl and aryl groups, respectively.

M represents a single-bond or divalent linker.

Q represents an alkyl group, a cycloalkyl group that may contain heteroatoms, or an aryl, amino, ammonium, teryl, cyano, or aldehyde group that may contain heteroatoms.

At least two of Q, M, and _L1 can be bonded to form a ring (preferably a 5- or 6-membered ring).

The repeating unit represented by the above general formula (VI) is preferably the repeating unit represented by the following general formula (3).

In general formula (3), Ar ₃ represents an aromatic cycloalloy.

R ₃ represents a hydrogen atom, alkyl, cycloalkyl, aryl, aralkyl, alkoxy, acetyl, or heterocyclic group.

_M3 represents a single-bond or dual-valent linker.

_Q3 indicates alkyl, cycloalkyl, aryl, or heterocyclic.

At least two of _Q3 , _M3 and _R3 can be bonded to form a ring.

Ar ₃ represents the same aromatic cyclic group as Ar ₆ in the above general formula (VI) when n is 1, with phenyl or naphthyl preferred, and phenyl preferred even more.

((The side chain contains repeating units of silicon atoms))

Resin P may also contain repeating units having silicon atoms in the side chains. Examples of repeating units having silicon atoms in the side chains include (meth)acrylate repeating units having silicon atoms and vinyl repeating units having silicon atoms. A repeating unit having silicon atoms in the side chain is typically a repeating unit having groups having silicon atoms in the side chain. Examples of groups having silicon atoms include trimethylsilyl, triethylsilyl, triphenylsilyl, tricyclohexylsilyl, tri-trimethylsiloxysilyl, tri-trimethylsilylsilyl, tri-trimethylsilylsilyl, methylbistrimethylsilylsilyl, methylbistrimethylsiloxysilyl, dimethyltrimethylsilylsilyl, dimethyltrimethylsiloxysilyl, and cyclic or linear polysiloxane or cage-type or ladder-type or random sesquioxane structures as described below. In the formula, R and ^R1 independently represent monovalent substituents. * indicates a bond.

[Chemical Formula 11]

As a repeating unit having the above-mentioned groups, it is preferable to use, for example, an acrylate compound having the above-mentioned groups, a repeating unit derived from a methacrylate compound, or a repeating unit derived from a compound having the above-mentioned groups and a vinyl group.

When resin P has repeating units with silicon atoms in its side chains as described above, the content of silicon atoms relative to the total repeating units in resin P is preferably 1-30 mol%, more preferably 5-25 mol%, and particularly preferably 5-20 mol%.

As a conversion value for polystyrene based on GPC (Gel permeation chromatography) method, a weight-average molecular weight (WM) of 1,000–200,000 is preferred, 3,000–20,000 is more preferred, and 5,000–15,000 is exceptionally preferred. Setting the WM to 1,000–200,000 helps prevent degradation of heat resistance and dry etching resistance, as well as degradation of developing properties or film-forming properties due to increased viscosity.

The dispersion (molecular weight distribution) is typically 1-5, with 1-3 being better, 1.2-3.0 being even better, and 1.2-2.0 being exceptionally good.

In the pharmaceutical solution, the content of resin P in the total solids is preferably 50-99.9% by mass, and even more preferably 60-99.0% by mass.

Furthermore, resin P can be used in the solution, either one type or multiple types.

Regarding other components contained in the pharmaceutical solution (such as acid generators, alkaline compounds, quenchers, hydrophobic resins, surfactants, and solvents), known formulations are permitted. Examples of pharmaceutical solutions include those contained in photosensitive or radiosensitive resin compositions as described in Japanese Patent Application Publication Nos. 2013-195844, 2016-057645, 2015-207006, International Publication No. 2014/148241, 2016-188385, and 2017-219818.

<Uses of the medicinal liquid>

The solution is preferred for use in the fabrication of semiconductor devices. It is particularly suitable for forming fine patterns (e.g., including steps involving EUV patterning) with nodes smaller than 10 nm.

The solution is a solvent (pre-wetting solution, developer, rinsing solution, solvent for photoresist, and stripping solution, etc.) used in resist processes where the pattern width and/or pattern spacing is 17 nm or less (preferably 15 nm or less, more preferably 12 nm or less) and/or the resulting wiring width and/or wiring spacing is 17 nm or less. In other words, it is particularly preferred for the manufacture of semiconductor devices using photoresist films with a pattern width and/or pattern spacing of 17 nm or less.

Specifically, in the manufacturing process of semiconductor devices, including lithography, etching, ion implantation, and peeling steps, this solution is used to treat organic matter after each step and before moving to the next. Preferably, it is used as a pre-wetting solution, developer, rinse solution, or peeling solution. For example, it can also be used to rinse the edges of semiconductor substrates before and after resist coating.

Furthermore, the aforementioned solution can also be used as a diluent for resins contained in photoresists, and as a solvent for photoresists. It can also be diluted using other organic solvents and/or water.

Furthermore, besides its use in the manufacture of semiconductor devices, the aforementioned solution can also be used for other applications, such as as a developing solution and rinsing solution for polyimide, sensor resists, lens resists, etc.

Furthermore, the aforementioned solution can also be used as a solvent for medical or cleaning purposes. In particular, it is well-suited for cleaning containers, piping, and substrates (e.g., wafers and glass).

The effect is further enhanced when the solution is used as a raw material selected from at least one liquid selected from the group consisting of developer, washing solution, wafer cleaning solution, wire cleaning solution, pre-wetting solution, photoresist, lower film forming solution, upper film forming solution, and hard coating forming solution.

[Method for manufacturing the liquid medicine]

There are no particular limitations on the method for manufacturing the aforementioned medicinal solution, and known manufacturing methods can be used. However, in terms of obtaining superior effects of the present invention, a filtration step that uses a filter to filter the purified substance containing the solvent to obtain the medicinal solution is preferable.

The purified material used in the filtration step can be purchased or obtained through a reaction of raw materials. As a purified material, a low impurity content is preferable. Commercially available products, for example, are labeled as "high purity grade products."

There are no particular limitations on the method for reacting raw materials to obtain a purified product (typically a purified product containing an organic solvent), and known methods can be used. For example, a method for obtaining an organic solvent by reacting one or more raw materials in the presence of a catalyst can be cited.

More specifically, examples include methods for reacting acetic _acid and n-butanol in the presence of sulfuric acid to obtain butyl acetate; methods for reacting ethylene, oxygen, and water in the presence of Al( _C₂H₅ ) _₃ to obtain 1-hexanol; methods for reacting cis-4-methyl-2-pentene in the presence of Ipc₂BH (Diisopinocampheylborane) to obtain 4-methyl-2-pentanol; methods for reacting propylene oxide, methanol, and acetic acid in the presence of sulfuric acid to obtain PGMEA (propylene glycol 1-monomethyl ether 2-acetic acid); and methods for reacting acetone and hydrogen in the presence of copper oxide-zinc oxide-aluminum oxide to obtain IPA (isopropyl) Methods for obtaining ethyl lactate by reacting lactic acid and ethanol (isopropanol); and methods for obtaining ethyl lactate by reacting lactic acid and ethanol; etc.

<Filtration Steps>

The method for manufacturing the pharmaceutical solution according to an embodiment of the present invention includes a filtration step of filtering the purified substance using a filter to obtain the pharmaceutical solution. There are no particular limitations on the method of filtering the purified substance using a filter, but it is preferable to pass the purified substance through (fluid-passing through) a filter unit having a shell and a filter element housed within the shell, whether under pressure or not.

(Diameter of the filter's pores)

There are no particular limitations on the pore diameter of the filter; filters with pore diameters commonly used for filtering purified substances can be used. However, in terms of making it easier to control the number of particles (including metal particles) contained in the drug solution within the desired range, a pore diameter of 200 nm or less is preferred, 20 nm or less is even better, 10 nm or less is further better, 5 nm or less is particularly good, and 3 nm or less is optimal. There are no particular limitations on the lower limit, but from a production standpoint, 1 nm or more is generally preferred.

Additionally, in this manual, the pore diameter and pore diameter distribution of the filter refer to _the pore diameter and pore diameter distribution determined by the bubble point of isopropanol (IPA) or HFE-7200 (“Novec 7200”, manufactured by 3M Company, _{hydrofluoroether} , _{C4F9OC2H5 )} .

If the pore diameter of the filter is 5.0 nm or less, it is better to control the number of particles in the drug solution more easily. Hereinafter, filters with a pore diameter of 5 nm or less will be referred to as "micropore filters".

Furthermore, micropore filters can be used alone or in conjunction with filters having other pore diameters. From a productivity standpoint, using them in conjunction with filters having larger pore diameters is preferable. In this case, passing the purified material, pre-filtered with a filter having larger pore diameters, through the micropore filter prevents clogging of the micropore filter.

In other words, when using a single filter, a pore diameter of 5.0 nm or less is preferred. When using two or more filters, the filter with the smallest pore diameter is preferably 5.0 nm or less.

There are no particular restrictions on the use of two or more filters with different pore diameters in sequence, but a method can be given as an example of arranging the filter units as described above sequentially along the pipeline that transports the purified material. In this case, if the flow rate of the purified material per unit time is to be set constant as a whole pipeline, sometimes a filter unit with a smaller pore diameter will exert greater pressure than a filter unit with a larger pore diameter. In this case, it is preferable to install pressure regulating valves and dampers between filter units to maintain a constant pressure on filter units with small pore diameters, or to arrange filter units containing identical filters side-by-side along the pipeline, thereby increasing the filtration area. This allows for more stable control of the number of particles in the drug solution.

(Filter material)

There are no particular limitations on the materials used in the filter; known materials can be used. Specifically, in the case of resins, examples include polyamides such as nylon (e.g., 6-nylon and 6,6-nylon); polyolefins such as polyethylene and polypropylene; polystyrene; polyimide; polyamide-imide; poly(meth)acrylate; polytetrafluoroethylene, perfluoroalkoxyalkylene, perfluoroethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-trifluorochloroethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride, etc., as well as polyfluorocarbons; polyvinyl alcohol; polyester; cellulose; cellulose acetate, etc. Of particular interest, in terms of superior solvent resistance and superior defect suppression properties of the obtained pharmaceutical solution, at least one polymer selected from the group consisting of nylon (preferably 6,6-nylon), polyolefins (preferably polyethylene), poly(meth)acrylates, and polyfluorocarbons (preferably polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkylene (PFA)). These polymers can be used alone or in combination of two or more.

In addition to resin, it can also be used to make diatomaceous earth and glass.

In addition, polymers obtained by graft copolymerization of polyamides (e.g., nylon-6 or nylon-6,6, etc.) with polyolefins (such as UPE described later) (nylon-grafted UPE, etc.) can be used as filter materials.

Furthermore, the filter can be a surface-treated filter. There are no particular limitations on the surface treatment method; well-known methods can be used. Examples of surface treatment methods include chemical modification, plasma treatment, hydrophobic treatment, coating, gas treatment, and sintering.

Plasma treatment hydrophilizes the filter surface, which is therefore preferable. There are no particular limitations on the water contact angle on the surface of the filter material hydrophilized by plasma treatment, but a static contact angle of 60° or less at 25°C, measured with a contact angle meter, is preferred, less than 50° is better, and less than 30° is exceptionally good.

As a chemical modification treatment, introducing ion exchange groups into the substrate is preferable.

That is, as a filter, it is preferable to use the materials mentioned above as substrates and introduce ion exchange groups into the substrates. Typically, a filter comprising a layer of substrate containing ion exchange groups on its surface is preferred. There are no particular limitations on the surface-modified substrate; however, for ease of manufacture, a filter that introduces ion exchange groups into the polymer is preferred.

Regarding ion exchange groups, examples of cation exchange groups include sulfonic acid groups, carboxyl groups, and phosphate groups, while examples of anion exchange groups include fourth-order ammonium groups. There are no particular limitations on the methods for introducing ion exchange groups into polymers; typical methods involve grafting by reacting compounds containing both ion exchange groups and polymerizable groups with the polymer.

There are no particular limitations on the method of introducing ion exchange groups. The resin fibers are irradiated with ionizing radiation (alpha, beta, gamma, X-rays, and electron beams, etc.) to generate active components (free radicals) in the resin. The irradiated resin is then immersed in a solution containing monomers, allowing the monomers to graft polymerize onto a substrate. As a result, the monomers form a polymer that bonds to polyolefin fibers as graft polymer side chains. The resin containing this generated polymer as a side chain is then reacted with a compound containing anion or cation exchange groups, introducing ion exchange groups into the graft polymer side chains to obtain the final product.

Furthermore, the filter can also be constructed by combining woven or non-woven fabrics with ion-exchange groups formed through radiation graft polymerization with conventional filter materials such as glass wool, woven or non-woven fabrics.

Using a filter containing ion-exchange groups makes it easier to control the concentration of metal-atom-containing particles in the drug solution within the desired range. There are no particular limitations on the materials used for filters containing ion-exchange groups, but examples include materials that incorporate ion-exchange groups into fluorocarbons and polyolefins; materials that incorporate ion-exchange groups into fluorocarbons are preferred.

There are no particular limitations on the pore diameter of the filter containing the ion exchanger, but 1-30 nm is preferred, and 5-20 nm is even better. The filter containing the ion exchanger can also be used as the filter with the smallest pore diameter as described above, or it can be used separately from the filter with the smallest pore diameter. From the perspective of obtaining superior performance of the present invention, it is preferable to use both a filter containing the ion exchanger and a filter without the ion exchanger and with the smallest pore diameter in the filtration step.

There are no particular limitations on the material used for the filter, which has been described as having the smallest pore diameter. However, from the viewpoint of solvent resistance, it is generally preferable to select at least one material from the group consisting of polyfluorocarbons and polyolefins, with polyolefins being more preferred.

Therefore, as the filter used in the filtration step, two or more filters made of different materials can be used. For example, two or more filters selected from the group consisting of polyolefins, polyfluorocarbons, polyamides, and materials incorporating ion exchange groups can be used.

(The fine pore structure of the filter)

There are no particular limitations on the pore structure of a filter; it can be appropriately selected based on the composition of the substance being purified. In this specification, the pore structure of the filter refers to the pore diameter distribution, the positional distribution of the pores within the filter, and the shape of the pores, which can typically be controlled through the filter's manufacturing method.

For example, porous membranes can be obtained by sintering powders such as resins, and fibrous membranes can be obtained by methods such as electrospinning, electroblowing, and meltblowing. The micropore structures of these methods are different.

A "porous membrane" refers to a membrane that retains components in a purified material, such as gels, particles, colloids, cells, and oligomers, but allows components smaller than the pore size to pass through. Sometimes, the retention of components in a purified material using a porous membrane depends on operating conditions, such as surface velocity, the use of surfactants, pH, and combinations thereof, and may also depend on the pore size and structure of the porous membrane, as well as the size and structure of the particles to be removed (hard particles or gels, etc.).

When the purified material contains negatively charged particles, polyamide filters function as non-screening membranes to remove these particles. Typical non-screening membranes include nylon-6 membranes and nylon-6,6 membranes, but are not limited to these.

Furthermore, the "non-sieve" based retention mechanism used in this manual refers to retention achieved through mechanisms such as obstruction, diffusion, and adsorption, which are independent of filter pressure reduction or pore size.

Non-sieve retention encompasses retention mechanisms that remove target particles from the purified material regardless of filter pressure reduction or pore size, including obstruction, diffusion, and adsorption. Particle adsorption on the filter surface can be mediated by intermolecular van der Waals forces and electrostatic forces. Particles moving within a non-sieve membrane layer with serpentine pathways may obstruct contact with the membrane if they cannot change direction sufficiently quickly. Diffusion-based particle transport is generated primarily by the random or Brownian motion of small particles, resulting in a probability of collision between particles and the filter material. Non-sieve retention mechanisms become active when no repulsive force exists between the particles and the filter.

UPE (ultra-high molecular weight polyethylene) filters are typically sieve membranes. A sieve membrane primarily refers to a membrane that traps particles through a sieving mechanism, or a membrane optimized for trapping particles through a sieving mechanism.

Typical examples of screen membranes include, but are not limited to, polytetrafluoroethylene (PTFE) membranes and UPE membranes.

Additionally, the "screening mechanism" refers to the ability to retain particles larger than the pore size of the porous membrane. Screening force can be enhanced by forming a filter cake (a condensation of particles on the membrane surface that become the target particles). The filter cake effectively performs the function of a secondary filter.

There are no particular limitations on the material of the fiber membrane, as long as it is a polymer capable of forming a fiber membrane. Examples of polymers include polyamide. Examples of polyamides include nylon 6 and nylon 6,6. Poly(ether monoxide) can be used as the polymer forming the fiber membrane. When the fiber membrane is located on the primary side of the porous membrane, it is preferable that the surface energy of the fiber membrane is higher than that of the polymer material of the porous membrane located on the secondary side. An example of such a combination is a case where the fiber membrane is made of nylon and the porous membrane is made of polyethylene (UPE).

There are no particular limitations on the manufacturing method of the fiber membrane; well-known methods can be used. Examples of manufacturing methods for fiber membranes include electrospinning, electric blowing, and meltblowing.

There are no particular limitations on the microporous structure of porous membranes (e.g., porous membranes containing UPE and PTFE). Examples of micropore shapes include lace-like, string-like, and nodular structures.

There are no particular restrictions on the size distribution and positional distribution of pores in a porous membrane. It can have a smaller size distribution and symmetrical positional distribution within the membrane. Alternatively, it can have a larger size distribution and asymmetrical positional distribution within the membrane (these membranes are also called "asymmetric porous membranes"). In asymmetric porous membranes, the pore size varies within the membrane; typically, the pore diameter increases from one surface to the other. In this case, the surface with more large-diameter pores is called the "open side," and the surface with more small-diameter pores is called the "tite side."

Furthermore, as an asymmetric porous membrane, one can cite an example where the pore size is smallest at a certain location within the membrane's thickness (this is also known as an "hourglass shape").

Using an asymmetric porous membrane with larger pore sizes on the primary side—in other words, making the primary side open—creates a pre-filtration effect.

Porous membranes can contain thermoplastic polymers such as PESU (polyethersulfone), PFA (a copolymer of perfluoroalkoxyalkylene, ethylene tetrafluoride, and perfluoroalkoxyalkylene), polyamide, and polyolefins, and may also contain polytetrafluoroethylene.

Among these, ultra-high molecular weight polyethylene (UHMWPE) is preferred as a material for porous membranes. UHMWPE refers to thermoplastic polyethylene with extremely long chains, and a molecular weight of over one million, typically 2-6 million, is preferred.

As filters used in the filtration process, two or more filters with different pore structures can be used, and filters using both porous membranes and fiber membranes can be used simultaneously. For example, a method using a nylon fiber membrane filter and a UPE porous membrane filter can be given.

Also, regarding the filter, it is best to clean it thoroughly before use.

When using an uncleaned filter (or a filter that has not been thoroughly cleaned), impurities contained in the filter can easily enter the drug solution.

Impurities contained in the filter, such as the aforementioned organic components, can sometimes lead to concentrations in the solution exceeding the permissible limits for the medicinal solution of this invention if an uncleaned filter (or an insufficiently cleaned filter) is used for filtration.

For example, when polyolefins such as UPE and polyfluorocarbons such as PTFE are used in filters, the filters are prone to containing alkanes with 12 to 50 carbon atoms as impurities.

Furthermore, when a filter is used to obtain a polymer formed by graft copolymerization of polyamide (such as nylon) with polyamides such as nylon, polyimide, and polyolefins (such as UPE), the filter is prone to containing olefins with 12 to 50 carbon atoms as impurities.

One method for cleaning the filter is, for example, immersing it in an organic solvent with low impurity content (e.g., a distilled and purified organic solvent (PGMEA, etc.)) for more than one week. In this case, a solvent temperature of 30–90°C is preferred.

The following adjustments can be made: Filter the purified material using a filter with an adjusted cleaning level, thereby ensuring the resulting solution contains the desired amount of organic components from the filter.

The filtration process can be a multi-stage filtration process that passes the purified material through at least two different filters selected from at least one different group of filters, including filter materials, pore sizes, and pore structures.

Furthermore, the purified substance can be passed through the same filter multiple times, or it can be passed through the same type of filter multiple times.

The material used for the wetted parts (inner wall surfaces, etc., that may come into contact with the purified substance and the chemical solution) of the purification apparatus used in the filtration step is not particularly limited, but it is preferable to use at least one material selected from the group consisting of non-metallic materials (such as fluoropolymers) and electrolytically polished metallic materials (such as stainless steel) (hereinafter, these will also be collectively referred to as "corrosion-resistant materials"). For example, the wetted parts of a manufacturing tank being formed of a corrosion-resistant material could be formed of a corrosion-resistant material itself, or the inner wall surfaces of the manufacturing tank being covered with a corrosion-resistant material.

There are no particular restrictions on the non-metallic materials used; any known materials can be used.

As a non-metallic material, examples include, but are not limited to, at least one selected from the group consisting of polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, and fluoropolymers (e.g., tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene-ethylene copolymer resin, trifluorochloroethylene-ethylene copolymer resin, vinylidene fluoride resin, trifluorochloroethylene copolymer resin, and fluoroethylene resin, etc.).

Furthermore, from the viewpoint of preventing static electricity in the liquid, materials treated with anti-static agents can be used as non-metallic materials. One method for implementing anti-static treatment is to use a conductive material together with the aforementioned non-metallic material (e.g., the aforementioned fluororesin).

The conductive material preferably contains carbon. From the viewpoint of better suppressing the charging of the liquid, carbon is preferably selected from at least one material including carbon particles (e.g., graphite, carbon black, acetylene black, Ketjen black), carbon nanotubes (e.g., graphene sheets formed into single or multilayer coaxial tubular structures, also known as CNTs), and carbon fibers.

There are no particular restrictions on the metal materials used; any known materials can be used.

As for metallic materials, examples include those where the combined chromium and nickel content exceeds 25% by mass of the total metallic material, with 30% or more being preferred. There is no particular upper limit to the combined chromium and nickel content in metallic materials, but it is generally preferred to be below 90% by mass.

As metallic materials, examples include stainless steel and nickel-chromium alloys.

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

There are no particular restrictions on the use of nickel-chromium alloys; any known nickel-chromium alloy can be used. However, nickel-chromium alloys with a nickel content of 40-75% by mass and a chromium content of 1-30% by mass are preferred.

Examples of nickel-chromium alloys include, for instance, Hoechst alloys (product name, hereinafter the same), Monel alloys (product name, hereinafter the same), and IngoNi alloys (product name, hereinafter the same). More specifically, examples include Hoechst alloy C-276 (Ni content 63% by mass, Cr content 16% by mass), Hoechst alloy-C (Ni content 60% by mass, Cr content 17% by mass), and Hoechst alloy C-22 (Ni content 61% by mass, Cr content 22% by mass).

In addition to the alloys mentioned above, nickel-chromium alloys may also contain boron, silicon, tungsten, molybdenum, copper, and cobalt, depending on the requirements.

There are no particular limitations on the method for electrolytic polishing of metallic materials, and known methods can be used. For example, the methods described in paragraphs [0011] to [0014] of Japanese Patent Application Publication No. 2015-227501 and paragraphs [0036] to [0042] of Japanese Patent Application Publication No. 2008-264929 can be used.

Regarding metallic materials, it is presumed that the chromium content in the passivation layer formed by electrolytic polishing becomes higher than that in the parent phase. Therefore, it is hypothesized that if a purification device with a wetted section made of electrolytically polished metallic material is used, metal particles would be difficult to flow into the purified solution.

In addition, metal materials can also be polished. There are no particular restrictions on the polishing method; well-known methods can be used. There are no particular restrictions on the size of the abrasive grains used in fine polishing, but from the perspective of minimizing surface roughness of the metal material, grits below #400 are preferred, 1000 to #400 are better, and #600 to #400 are even better. Polishing is best performed before electrolytic polishing.

Furthermore, metallic materials can also undergo acid treatment and/or passivation. These treatments are preferably performed after electrolytic polishing.

Polishing, acid treatment, and passivation can be performed individually or in combination of two or more processes.

<Other steps>

The manufacturing method of the pharmaceutical solution can also include steps other than filtration. Examples of steps other than filtration include distillation, reaction, and electrostatic removal.

(Distillation steps)

The distillation step is the process of distilling a purified substance containing an organic solvent to obtain a distilled purified substance. There are no particular limitations on the method used to distill the purified substance, and known methods can be used. Typically, a method can be described by arranging a distillation column on the primary side of a purification apparatus for the filtration step, and introducing the distilled purified substance into a manufacturing tank.

At this point, there are no particular restrictions on the receiving section of the distillation tower, but it is preferable to use a corrosion-resistant material as described above.

(Reaction Steps)

A reaction step is a step in which raw materials react to produce a purified product containing an organic solvent as a reactant. There are no particular limitations on the method for producing the purified product, and known methods can be used. Typically, a method is described where a reaction vessel is arranged on the primary side of a purification apparatus for a filtration step, and the reactants are introduced into the vessel (or distillation column).

At this point, there are no particular restrictions on the material used for the receiving portion of the vessel, but it is preferable to use a corrosion-resistant material as described above.

(Except for electric steps)

The charge removal step is the process of removing charge from the substance being purified, thereby reducing the charged potential of the substance.

There are no particular limitations on the method of static removal; any known static removal method can be used. For example, a method of static removal could be to bring the purified material into contact with a conductive material.

The contact time between the purified material and the conductive material is preferably 0.001 to 60 seconds, more preferably 0.001 to 1 second, and exceptionally preferably 0.01 to 0.1 seconds. Examples of conductive materials include stainless steel, gold, platinum, diamond, and glassy carbon.

One method for bringing the purified material into contact with the conductive material is, for example, arranging a grounded mesh made of conductive material within a conduit and allowing the purified material to pass through it.

Regarding the purification of the substance being purified, it is preferable that all processes, including opening the accompanying containers, cleaning the containers and apparatus, containing the solution, and analysis, be carried out in a cleanroom. The cleanroom should ideally be at least level 4 as specified in the international standard ISO 14644-1:2015, as defined by the International Organization for Standardization (ISO). Specifically, meeting any one of ISO Level 1, ISO Level 2, ISO Level 3, or ISO Level 4 is preferred; meeting ISO Level 1 or ISO Level 2 is even better; and meeting ISO Level 1 is exceptionally good.

There are no particular restrictions on the storage temperature of the medicinal solution. However, since small amounts of impurities in the solution are difficult to dissolve, a storage temperature of 4°C or higher is preferable to achieve the superior effects of this invention.

[Container]

The container holds the aforementioned liquid medicine. When storing or transporting the liquid medicine container, the inner container of the liquid medicine container must be sealed to contain the liquid medicine and prevent leakage to the outside of the container.

Store the liquid medicine in a container until use. When using the medicine, remove it from the container.

For semiconductor device manufacturing applications, a high degree of cleanliness and minimal leaching of impurities are preferred when using a container.

As containers, examples include AICELLO CHEMICAL CO.,LTD.'s "Clean Bottle" series and KODAMA PLASTICS CO.,LTD.'s "Pure Bottle," but these are not the only examples.

As a container, it is preferable to use a multilayer bottle with an inner wall constructed of a six-layer structure based on six resins or a seven-layer structure based on six resins, for the purpose of preventing impurities (contamination) from entering the liquid medicine. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

At least a portion of the wetted portion of the container can be made of a corrosion-resistant material as described above (preferably electrolytically polished stainless steel or fluororesin) or glass. From the perspective of obtaining superior effects of the invention, it is preferable that more than 90% of the wetted portion area is formed of the aforementioned material, and even more preferably, the entire wetted portion is formed of the aforementioned material.

One preferred embodiment of the container is one in which at least a portion of the liquid-contacting part is made of electrolytically polished stainless steel. In this case, an average surface roughness Ra of the liquid-contacting part of the container is preferably 1500 nm or less; from the perspective of better defect suppression performance and better suppression of drug charge, less than 100 nm is preferred, less than 10 nm is more preferred, and less than 5 nm is even more preferred. Furthermore, a lower limit for the average surface roughness Ra of the liquid-contacting part of the container is preferably 1 nm or more.

The average surface roughness Ra of the wetted portion of the container can be measured as follows: First, using an atomic force microscope (AFM) with a cantilever of 10 nm probe diameter, the surface shape is measured to obtain three-dimensional data. Specifically, the wetted portion of the container is cut into 1 cm angle pieces and placed on a horizontal sample stage of a piezoelectric scanner. The cantilever is brought close to the sample surface, reaching the region where interatomic forces are active. The results are scanned along the XY directions. The unevenness of the sample is captured by the piezoelectric displacement in the Z direction. During measurement, 512 × 512 points are measured within a 5 μm × 5 μm area on the surface. Using the three-dimensional data (f(x,y)) obtained above, the average surface roughness Ra is calculated.

Furthermore, as one preferred embodiment of the container, at least a portion of the liquid-receiving part of the container, along with the aforementioned fluoropolymer resin, may also include a conductive material. This further suppresses the charging of the liquid. Specific examples of the conductive material are the same as those described in the corrosion-resistant materials already explained.

The porosity of the container within the drug solution containment body is preferably 50-99.99% by volume, more preferably 50-99.90% by volume, and exceptionally preferably 80-99% by volume. If the porosity is within this range, the drug solution can be easily handled due to the adequate space provided.

Furthermore, the aforementioned porosity is calculated according to the following formula (X).

Formula (X): Porosity (volume %) = {1 - (volume of liquid in container / volume of container)} × 100

The container volume mentioned above has the same meaning as the internal volume (capacity) of a container.

The voids within the container of the liquid contain gas containing an organic compound (specific organic compound B, described later) with a ClogP value higher than that of the solvent.

The gas is usually air, but it is preferable that at least a portion of the air is replaced by nitrogen. If at least a portion of the air is replaced by nitrogen, the content of organic compound B present in the pores can be controlled, thus yielding a solution with excellent defect suppression performance.

To maximize the effectiveness of this invention, a nitrogen content of 95-99.9999% of the total volume of the container's voids is preferable, and 97-99.99% is even better.

<Specific organic compound B>

The gas present in the pores of the container contains a specific organic compound B. This specific organic compound B, as described above, is an organic compound whose ClogP value in the pharmaceutical solution is higher than that of the solvent.

The preferred form and specific examples of the ClogP value for a particular organic compound B are the same as those for a particular organic compound A.

The total content of specific organic compound A and specific organic compound B relative to the total mass of the drug solution should be less than 100,000 ppt, with 0.1 to 100,000 ppt being preferred.

If the total amount of the above-mentioned components is less than 100,000 ppt by mass, it can inhibit specific organic compounds from becoming defects, thus obtaining a drug solution with excellent defect inhibition performance.

Furthermore, if the total content of the above-mentioned substances is 0.1 ppt or more, the generation of defects based on metal-containing particles can be suppressed by the action of specific organic compounds. While the detailed reasoning is unclear, it can be inferred that the specific organic compounds in the solution inhibit the aggregation of metal-containing particles or the retention of metal-containing particles on the wiring substrate. This effect is particularly significant when forming the aforementioned micro-patterns.

To further enhance the aforementioned effects, the upper limit of the total amount of the above-mentioned content is preferably below 100,000 mass ppt, even better below 2,000 mass ppt, further better below 1,000 mass ppt, and exceptionally good below 10 mass ppt.

To maximize the aforementioned effects, a lower limit of 0.1 ppt or higher for the total content is preferable.

The content and type of a specific organic compound B in a gas can be measured using GCMS (gas chromatography-mass spectrometry).

From the perspective of superior defect suppression performance, the content of a specific organic compound B relative to the total mass of the drug solution is preferably below 50,000 ppt, better is 0.05~50,000 ppt, further better is 0.05~500 ppt, and exceptionally good is 0.05~5 ppt.

The mass ratio of the total content of specific organic compound A and specific organic compound B to the content of metal particles [(specific organic compound A + specific organic compound B) / metal particles] is preferably 0.01 to 100,000, more preferably 0.1 or higher, even better 10,000 or lower, and particularly preferred 1,000 or lower.

If the above-mentioned mass ratio is 0.01 or higher, the generation of defects based on metal-containing particles can be suppressed by the action of a specific organic compound. While the detailed reasoning is unclear, it can be inferred that the specific organic compound in the solution inhibits the aggregation of metal-containing particles or their residue on the wiring substrate. This effect is particularly significant when forming the aforementioned micro-patterns.

If the above mass ratio is 100,000 or less, it can suppress the formation of defects in specific organic compounds or the generation of composite particles of specific organic compounds and metal-containing particles, thus yielding a solution with excellent defect suppression performance.

The mass ratio (specific organic compound A/specific organic compound B) of 1 or more is preferred, 10 or more is even better, and 1,000 or more is exceptionally preferred.

If the above mass ratio is 1 or higher, the defect suppression performance over time (i.e., the defect suppression performance when using the medicine after long-term storage of the medicine container) is excellent.

There is no specific upper limit to the above mass ratios, but they are mostly below 10,000.

The preferred form of specific organic compound B is the same as that of specific organic compound A described above, wherein phthalate esters are preferred, and preferably selected from at least one of the group consisting of dioctyl phthalate (DOP) and diisononyl phthalate (DINP).

When the solution container contains both DOP and DINP, a mass ratio (DOP/DINP) of 1 or more, preferably 5 or more, of DOP to DINP in the solution container is preferable. DINP has a higher boiling point than DOP, therefore it is considered more likely to remain as a defect when adhering to a silicon substrate. However, a mass ratio of 1 or more results in a solution with superior defect suppression performance.

Furthermore, there is no particular upper limit to the above-mentioned mass ratio (DOP/DINP), but 10,000 or less is preferred, and 1,000 or less is even better.

[Implementation Example]

The present invention will now be described in further detail based on embodiments. The materials, quantities, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limited to the embodiments shown below.

Furthermore, in the preparation of the pharmaceutical solutions for both the embodiments and comparative examples, the handling of containers, preparation, filling, storage, and analytical measurements of the pharmaceutical solutions were all performed in a cleanroom meeting ISO Class 2 or 1 standards. To improve measurement accuracy, in the measurements of organic and metallic content—specifically, measurements of components below their limits—the pharmaceutical solution was concentrated, and the concentration was calculated by converting the measured content to the concentration of the solution before concentration.

[Medicinal Solution]

(Filter)

The filters used in the purification of the pharmaceutical solution were all cleaned with a cleaning solution prepared by distilling and purifying commercially available PGMEA (propylene glycol monomethyl ether acetate). Furthermore, regarding immersion, the entire filter unit containing the filter was immersed in PGMEA to clean all contact points. The immersion period was set to be at least one week. During immersion, the temperature of the PGMEA solution was maintained at 30°C.

The following filters were used as filters.

• UPE: Ultra-high molecular weight polyethylene filter, manufactured by Entegris Inc., with a pore size of 3 nm

• PTFE: Polytetrafluoroethylene filter, manufactured by Entegris Inc., with a pore size of 10 nm

• Nylon: Nylon filter, manufactured by PALL, with a pore size of 5nm

• Nylon-grafted UPE: A filter made of nylon/ultra-high molecular weight polyethylene graft copolymer, manufactured by Entegris Inc., with a pore size of 3nm.

• Polyimide: Polyimide filters, manufactured by Entegris Inc., with a pore size of 10 nm

[Purified substance]

To manufacture the pharmaceutical solutions of the embodiments and comparative examples, the following organic solvents were used as the purified substances. All of the following organic solvents were commercially available. Specifically, “PGMEA/PGME(7:3)” and “PGMEA/PC(9:1)” were purchased as pre-mixing organic solvents and mixed in prescribed quantities to obtain the purified substances.

• 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): A 7:3 (v/v) mixture of PGMEA and PGME (propylene glycol monomethyl ether, ClogP value = -0.20)

• PGMEA/PC (9:1): A 9:1 (v/v) mixture of PGMEA and PC (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 monoxide, 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

Cyclobutrazol, ClogP value = -0.78

Cycloheptanone, ClogP = 1.48

2-Hepanotone, ClogP value = 1.91

Butyl butyrate, ClogP value = 1.78

Isobutyl isobutyrate, ClogP value = 4.4

Undecane, ClogP value = 6.5

Amyl propionate, ClogP value = 2.8

Isoamyl propionate, ClogP value = 2.70

Ethylcyclohexane, ClogP value = 4.4

Mesitylene, ClogP value = 3.6

Decane, ClogP value = 6.0

[Purification Treatment]

One of the above-mentioned substances to be purified was distilled, and the purified substance was then passed through a filter that had undergone the above-mentioned cleaning process at least once for further purification.

Furthermore, during the series of purification processes, the piping used to transfer the purified substance and the chemical solution employed either stainless steel piping with electrolytically polished wetted surfaces or stainless steel piping that had not undergone electrolytic polishing.

By appropriately varying the type of purified substance, the type of filter, the filter cleaning period, the number of flushing cycles, the type of piping, and the length of the piping (based on the distance of piping transfer), the drug solutions shown in Tables 1 and 2 were prepared.

[Container]

As containers for storing liquid medicine, containers with the liquid-receiving parts made of materials listed in Table 1 or Table 2 were used.

PFA: Perfluoroalkoxyalkylene hydrocarbons

PTFE: Polytetrafluoroethylene

SUS316L-EP: Austenitic stainless steel (electrolytic polishing performed)

HDPE: High-density polyethylene

SUS304-EP: Austenitic stainless steel (electrolytic polishing performed)

SUS304: Austenitic stainless steel (not electrolytically polished)

.Glass

• PTFE and CNT: Materials containing polytetrafluoroethylene and carbon nanotubes

• PTFE and carbon particles: Materials containing polytetrafluoroethylene and carbon particles

• PTFE and carbon fiber: Materials containing polytetrafluoroethylene and carbon fiber

Additionally, regarding some embodiments in Table 2, such as SUS316L-EP, polishing (grit size: #400) was performed as a pretreatment before electropolishing and/or acid treatment (cleaning the contact area with a 7% nitric acid dilution) was performed as a posttreatment after electropolishing.

Furthermore, regarding the containers shown in Table 2, the average surface roughness Ra of the liquid-contacting portion of the containers was measured using the method described above.

First, a container was placed inside a 1,000L vacuum dryer. All components that might come into contact with the liquid, including the vacuum dryer, the container's receiving portion, and the piping used to allow the liquid to flow into the container, were cleaned with semiconductor-grade hydrogen peroxide solution. Then, the air inside the vacuum dryer was replaced with nitrogen for drying.

Next, after creating a vacuum state inside the vacuum dryer, repeated processes such as filling with nitrogen are performed to ensure a clean environment inside the dryer.

[Drug Containment Container]

The purified medicinal liquid, as described above, was contained in a container placed inside a vacuum dryer in a clean state, with the container porosity set as shown in Tables 1 and 2. Furthermore, the container was sealed to prevent the medicinal liquid from leaking out, thus obtaining a medicinal liquid container.

[Measurement of the content of various components in the drug solution container]

The following method was used to measure the content of each component in the liquid solution container. Furthermore, the following measurements were performed in a cleanroom that met ISO (International Organization for Standardization) level 2 or lower. To improve measurement accuracy, for each component, measurements were performed below the detection limit under normal conditions, by converting the volume to 1/100th concentration, and then converting this to the content of organic solvent before concentration to calculate the content. The results are shown in Tables 1 and 2.

Furthermore, measurements of the content of each component within the liquid medicine container are performed immediately after manufacturing (meaning immediately after the liquid medicine is contained in the container and immediately sealed).

[Organic compounds]

The content of organic compounds (specific organic compound A) in each drug solution whose ClogP value was higher than that of the organic solvent was measured using a gas chromatography-mass spectrometry (GCMS-2020, manufactured by Shimadzu Corporation, measurement conditions as follows).

Furthermore, the content of organic compounds (specific organic compound B) with ClogP values higher than those of the organic solvent, contained in the gas within the pores of the drug solution container, was also measured using the aforementioned gas chromatography-mass spectrometry analysis apparatus.

<Measurement Conditions>

Capillary column: InertCap 5MS/NP 0.25mm I.D. × 30m df = 0.25μm

Sample introduction method: constant pressure at 75 kPa during shunt flow

Vaporization chamber temperature: 230℃

Column oven temperature: 80℃ (2 min) - 500℃ (13 min) Heating rate: 15℃/min

Carrier gas: Helium

Spacing pad purging flow rate: 5 mL/min

Flow split ratio: 25:1

Interface temperature: 250℃

Ion source temperature: 200℃

Measurement mode: Scan m/z = 85~500

Sample volume: 1 μL

Based on the measured concentrations of specific organic compound A in the liquid and specific organic compound B in the gas, as described above, the mass of specific organic compound A and the mass of specific organic compound B in the liquid container were calculated.

Furthermore, the ratio of the mass of a specific organic compound A in the drug solution container to the mass of the drug solution in the drug solution container (i.e., the "content of specific organic compound A relative to the total mass of the drug solution (mass ppm)") was calculated, and the values are shown in the "Content of Specific Organic Compound A" column in Tables 1 and 2.

Similarly, the ratio of the mass of a specific organic compound B in the drug solution container to the mass of the drug solution in the drug solution container was calculated (i.e., the "content of the specific organic compound B relative to the total mass of the drug solution (mass ppm)"). The values are shown in the "Content of Specific Organic Compound B" column in Tables 1 and 2.

Furthermore, the "Total Content of Specific Organic Compound A and Specific Organic Compound B" in Tables 1 and 2 is the sum of the "Content of Specific Organic Compound A" and the "Content of Specific Organic Compound B" in Tables 1 and 2.

Similarly, the total content (mass ppt) of specific organic compounds A1 with a ClogP value of 6 or higher in specific organic compound A and specific organic compound B1 with a ClogP value of 6 or higher in specific organic compound B relative to the total mass of the drug solution was calculated. The results are shown in the "Total amount of specific organic compounds with a ClogP value of 6 or higher" column of Tables 1 and 2.

Similarly, the total content (mass ppt) of phthalates in specific organic compound A and specific organic compound B relative to the total mass of the drug solution was determined. The results are shown in the "Total Phthalate Content" column of Tables 1 and 2.

Similarly, the total content (mass ppt) of dioctyl phthalate (DOP) and diisononyl phthalate (DINP) in specific organic compound A and the total content (mass ppt) of DOP and DINP in specific organic compound B relative to the total mass of the drug solution were determined. The results are shown in the "Total Content (mass ppt)" column of "DINP and DOP" in Tables 1 and 2.

Furthermore, the mass ratio of the content (mass) of specific organic compound B in the drug solution container to the content (mass) of specific organic compound A in the drug solution container was calculated. The results are shown in the "Mass ratio of specific organic compound A to specific organic compound B" column of Tables 1 and 2.

Furthermore, the mass ratio of DOP content (by mass) to DINP content (by mass) in the drug solution container was calculated. The results are shown in the "DOP/DINP content" column of Tables 1 and 2.

[Particles containing metal]

The content of metal particles in the drug solution was measured using SP-ICP-MS.

The following devices were used. The results are shown in Tables 1 and 2.

Manufacturer: PerkinElmer Co., Ltd.

Model: NexION350S

The following parsing software was used in the parsing process.

• “SP-ICP-MS” Dedicated Syngistix Nano Application Module

Furthermore, the mass ratio of the total content of specific organic compound A and specific organic compound B in the drug solution container to the mass content (mass) of metal-containing particles in the drug solution was calculated. The results are shown in the "Ratio of Metal-Containing Particles to Specific Organic Compounds" column of Tables 1 and 2.

[Metal nanoparticles]

The number of metal nanoparticles (metal-containing particles with a diameter of 0.5–17 nm) in the drug solution was measured using the following method.

First, a certain amount of reagent was coated onto a silicon substrate to form a reagent-coated substrate. The surface of the reagent-coated substrate was scanned with laser light, and the scattered light was detected. This determined the location and particle size of defects on the surface of the reagent-coated substrate. Next, elemental analysis was performed using EDX (Energy Dispersive X-ray) analysis based on the location of these defects to examine their composition. Using this method, the number of metal nanoparticles on the substrate was determined and converted into the number of particles per unit volume of reagent (particles/ ^cm³ ).

In addition, the analysis combined the use of the KLA-Tencor Corporation's SP-5 wafer inspection system and the Applied Materials SEMVision G6 fully automated defect inspection and classification system.

Furthermore, for samples where the desired particle size cannot be detected using the resolution of the measuring device, the method described in paragraphs 0015 to 0067 of Japanese Patent Application Publication No. 2009-188333 was used for detection. Specifically, a _SiO₂ layer was formed on a substrate using CVD (chemical vapor deposition), and then a liquid coating was formed over the aforementioned layer. Next, a method was used in which the composite layer having the _SiO₂ layer and the liquid coating thereon was dry-etched, the resulting protrusion was irradiated with light, the scattered light was detected, the volume of the protrusion was calculated from the scattered light, and the particle size was calculated from the volume of the protrusion.

[Evaluation of Defect Suppression Performance]

The drug solution was removed from its container and used as a pre-humidifying solution to evaluate its defect suppression performance.

Regarding defect suppression performance, evaluations were conducted using both solutions immediately after manufacturing the drug container (meaning the drug was contained in the container and immediately sealed; indicated as "immediately after containment" in the table) and solutions stored at 50°C for one year (indicated as "after time" in the table).

In addition, the photoresist components used are as follows.

[Photoresist Component 1]

The photoresist composition 1 was obtained by mixing the various components in the following configuration.

Resin (A-1): 0.77g

Acid-producing agent (B-1): 0.03g

Alkaline compound (E-3): 0.03g

˙PGMEA: 67.5g

˙EL：75g

<Resin (A), etc.>

(Synthetic Example 1) Synthesis of Resin (A-1)

600 g of cyclohexanone was added to a 2 L flask, and nitrogen purging was performed for 1 hour at a flow rate of 100 mL/min. Then, 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 to 80 °C. Next, the 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 added dropwise to the flask heated to 80 °C over 6 hours. After the dropwise addition was completed, the reaction was carried out at 80 °C for another 2 hours.

4-Ethyloxystyrene 48.66 g (0.3 mol)

1-Ethylcyclopentyl methacrylate 109.4 g (0.6 mol)

Monomer 1: 22.2 g (0.1 mol)

The reaction solution was cooled to room temperature and added dropwise to 3 L of hexane to precipitate the polymer. The filtered solid was dissolved in 500 mL of acetone and added dropwise again to 3 L of hexane. The filtered solid was then dried under reduced pressure to obtain 160 g of 4-acetylated styrene/1-ethylcyclopentyl methacrylate/monomer 1 copolymer (A-1).

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 cooled to room temperature and added dropwise to 3 L of distilled water. The filtered solid was dissolved in 200 mL of acetone and added dropwise again to 3 L of distilled water. The filtered solid was then dried under reduced pressure to obtain resin (A-1) (8.5 g). The weight-average molecular weight (Mw) of standard polystyrene, converted from standard polystyrene by gel osmosis chromatography (GPC) (solvent: THF (tetrahydrofuran)), was 11200, and the molecular weight dispersion (Mw/Mn) was 1.45. The structure of resin A-1 is shown below.

<Photosensitive Acid Generator (B)>

The following were used as photosensitive acid generators.

<Alkaline Compounds (E)>

The following were used as alkaline compounds.

[Chemical Formula 15]

(Residue defect suppression performance, bridging defect suppression performance, and stain defect suppression performance)

The residue defect suppression performance, bridging defect suppression performance, and stain defect suppression performance of the coating solution were evaluated using the following methods. Additionally, the Tokyo Electron Limited coating/developing machine "LITHIUS (registered trademark) Pro Z" was used in the experiment.

First, AL412 (manufactured by BREWER SCIENCE, INC.) was coated on a silicon wafer and baked at 200°C for 60 seconds to form a 20nm thick photoresist lower layer. A pre-wetting solution (solution 1) was then coated on top, followed by photoresist composition 1, and baked at 100°C for 60 seconds (PB: Prebake) to form a 30nm thick photoresist film.

The photoresist film was exposed using an EUV exposure machine (ASML NXE3350, NA 0.33, Dipole 90°, outer sigma 0.87, inner sigma 0.35) through a reflective mask with a 20nm gap and a pattern width of 15nm. It was then heated at 85°C (Post Exposure Bake) for 60 seconds. Next, it was developed in an organic solvent-based developer for 30 seconds and rinsed for 20 seconds. Finally, the wafer was rotated at 2000 rpm for 40 seconds, thereby forming a line and space pattern with a 20nm gap and a 15nm linewidth.

Images of the aforementioned pattern were acquired and analyzed using a combination of the KLA-Tencor Corporation's SP-5 wafer inspection system and Applied Materials' SEMVision G6 fully automated defect inspection and classification system. The amount of residue per unit area of unexposed area was measured.

Furthermore, for samples where the desired particle size cannot be detected using the resolution of the measuring device, the method described in paragraphs 0015 to 0067 of Japanese Patent Application Publication No. 2009-188333 was used for detection. Specifically, a _SiO₂ layer was formed on a substrate using CVD (chemical vapor deposition), and then a liquid coating was formed over the aforementioned layer. Next, a method was used in which the composite layer having the _SiO₂ layer and the liquid coating thereon was dry-etched, the resulting protrusion was irradiated with light, the scattered light was detected, the volume of the protrusion was calculated from the scattered light, and the particle size was calculated from the volume of the protrusion.

The evaluation was conducted using the following criteria, and the results are shown in Tables 1 and 2.

A: The number of defects is less than 60.

B: The number of defects is more than 60 but less than 90.

C: The number of defects is more than 90 but less than 120.

D: The number of defects is more than 120 but less than 150.

E: The number of defects is more than 150 but less than 180.

(Charged)

The electrical charge on the liquid surface immediately after filling with the solution was measured using a KASUGA DENKI, Inc. KSD-2000 digital electrostatic potential meter. The results were evaluated using the following criteria and are shown in Table 2.

A: The voltage is within ±2kV.

B: The voltage level is outside the ±2kV range but within the ±10kV range.

C: The voltage level is outside the ±10kV range.

In Tables 1 and 2 above, the values recorded in the column “Number of metal nanoparticles” are abbreviated exponents. For example, “1.00E+05” means “1.00× ^10⁵ ”.

As shown in Tables 1 and 2, if the content of metal particles relative to the total mass of the drug solution is 10 ppt or less, and the combined content of specific organic compound A and specific organic compound B relative to the total mass of the drug solution is 100,000 ppt or less, then the defect suppression performance is excellent even when using the drug solution taken out at any time after it has been contained in the drug solution container or after long-term storage (Example).

Furthermore, a comparison between Examples 1 and 2 and Example 7 shows that if the content of metal particles relative to the total mass of the liquid is within the range of 0.1 to 10 ppt (Examples 1 and 2), the defect suppression performance is superior even when the liquid is taken out at any time after being contained in the liquid container or after long-term storage.

Furthermore, a comparison between Embodiment 3 and Embodiment 19 shows that if the content of metal particles relative to the total mass of the liquid is less than 1 ppt (Embodiment 19), the defect suppression performance is superior even when the liquid is taken out at any time after being contained in the liquid container or after long-term storage.

Furthermore, a comparison between Embodiment 4 and Embodiment 19 shows that if the total content of specific organic compound A and specific organic compound B is less than 2,000 mass ppt relative to the total mass of the drug solution (Embodiment 19), then the defect suppression performance is superior, even when the drug solution is taken out at any time after being contained in the drug solution container or after long-term storage.

Furthermore, a comparison between Embodiment 5 and Embodiment 19 shows that if the mass ratio of the total content of specific organic compound A and specific organic compound B to the content of metal particles is 0.1 or more (Embodiment 19), then the defect suppression performance is superior when using the drug solution taken out at least once after being contained in the drug solution container and after long-term storage.

Furthermore, a comparison between Embodiment 6 and Embodiment 19 shows that if the mass ratio of the total content of specific organic compound A and specific organic compound B to the content of metal particles is 100,000 or less (Embodiment 19), then the defect suppression performance is excellent even when the drug solution is used at any time after being contained in the drug solution container or after long-term storage.

Furthermore, a comparison between Embodiment 8 and Embodiment 11 shows that if the mass ratio of a specific organic compound B to a specific organic compound A is 1 or more (Embodiment 11), the defect suppression performance of the drug solution after long-term storage is superior.

Furthermore, the comparison in Examples 9-12 shows that if the porosity of the container in the liquid medicine container is within the range of 50-99.99% by volume (Examples 9 and 11), the defect suppression performance of the liquid medicine after long-term storage is superior.

A comparison between Examples 15 and 16 shows that if the mass ratio (DOP/DINP) of dioctyl phthalate to diisononyl phthalate is 1 or more (Example 15), the defect suppression performance is superior when the drug solution is removed after long-term storage in the drug solution container.

As shown in Table 2, comparing Examples 102 to 106, if the liquid-contacting part of the container is made of electrolytically polished stainless steel and the average surface roughness Ra of the liquid-contacting part is less than 100 nm, then the defect suppression performance is superior (Example 102).

As shown in Table 2, comparing Examples 101 with Examples 107-109, the use of a liquid-contact portion incorporating a conductive material along with the fluororesin further suppresses the charging of the liquid.

On the other hand, as shown in Table 1, if the total content of metal particles in the liquid medicine, or the total content of specific organic compound A and specific organic compound B, falls outside the aforementioned range, then even if the liquid medicine is used at any time after being contained in the liquid medicine container or after long-term storage, the defect suppression performance is poor (comparative example).

(Implementation Example 34)

Regarding the PGMEA used in Example 15, repeated distillation and filtration were performed to produce a solution containing a specific organic compound at a concentration of less than 0.1 ppt by mass.

8000 ppt of dibutyl phthalate (manufactured by Wako Pure Chemical, Ltd.) was added to the drug solution, and the resulting drug solution was repeatedly filtered and contained in a container (the same container as in Example 15) to obtain the drug solution container of Example 34. In the drug solution container of Example 34, the content of specific organic compound A composed of dibutyl phthalate is 4800 ppt by mass, and the content of specific compound B composed of dibutyl phthalate is 10 ppt by mass.

The same evaluation results as in Example 15 were obtained using the liquid contained in the liquid container of Example 34. The defect suppression performance of the liquid container after being stored at 50°C for one year was rated as "C". Otherwise, the same results as in Example 15 were obtained.

without.

Claims (12)

A pharmaceutical liquid container includes a container and a pharmaceutical liquid contained within the container. The pharmaceutical liquid contains a solvent, metal-containing particles containing metal atoms, and an organic compound with a ClogP value higher than that of the solvent. The content of the metal-containing particles relative to the total mass of the pharmaceutical liquid is less than 10 mass ppt. A gas containing the organic compound with a ClogP value higher than that of the solvent is present in the pores of the container. The total content of the organic compound in the gas and the organic compound in the liquid is less than 100,000 ppt relative to the total mass of the liquid. Both the organic compound in the gas and the organic compound in the liquid contain phthalates. The solvent is an organic solvent. At least a portion of the liquid-receiving part of the container is electrolytically polished stainless steel, and the average surface roughness Ra of the liquid-receiving part of the container is 1 nm to 10 nm. As described in claim 1, the liquid container contains metal particles at a concentration of 0.001 ppt to 10 ppt relative to the total mass of the liquid, and the total concentrations of the organic compound in the gas and the organic compound in the liquid are 0.1 ppt to 100,000 ppt relative to the total mass of the liquid. As described in claim 1 or 2, the mass ratio of the total content of the organic compound in the gas and the organic compound in the liquid to the content of the metal particles is 0.01 to 100,000. As described in claim 1 or 2, the liquid container, wherein the ClogP value of both the organic compound in the gas and the organic compound in the liquid is 6 or higher. As described in claim 1 or 2, the phthalate ester comprises at least one selected from the group consisting of dioctyl phthalate and diisononyl phthalate. As described in claim 5, the liquid container contains a drug solution in a mass ratio of dioctyl phthalate to diisononyl phthalate of at least 1. As described in claim 1 or 2, the liquid container contains an organic compound in a liquid at a mass ratio of 1 or more to the organic compound in a gas. As described in claim 1 or 2, the organic solvent is selected from at least one of the following: 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, cyclobutanone, cycloheptanone, 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, amyl propionate, isoamyl propionate, ethylcyclohexane, mesitylene, and decane. As described in claim 1 or 2, the number of metal nanoparticles with a particle size of 0.5 nm to 17 nm in the metal-containing particles per unit volume of the drug solution is 1.0 × ^10¹ particles/ ^cm³ to 1.0 × ^10⁹ particles/ ^cm³ . As described in claim 1 or 2, the liquid container contains nitrogen gas, the nitrogen content being 95% to 99.9999% of the total volume of the pores, and the organic compound content in the gas being 0.05 to 50,000 ppt of the total mass of the liquid. As described in claim 1 or 2, the liquid medicine container within the liquid medicine container has a porosity of 50% to 99.99% by volume. The liquid container as described in claim 1 or 2, wherein the liquid is used as a raw material selected from at least one liquid selected from the group consisting of developer, washing solution, wafer cleaning solution, wire cleaning solution, pre-wetting solution, photoresist, lower film forming solution, upper film forming solution, and hard coating forming solution.