阅读说明：本技术 部件、容器、药液收容体、反应槽、蒸馏塔、过滤器单元、存储罐、管路、药液的制造方法 (Member, container, chemical liquid container, reaction tank, distillation column, filter unit, storage tank, pipeline, and method for producing chemical liquid ) 是由 清水哲也 上村哲也 高桥智美 大松祯 于 2019-07-05 设计创作，主要内容包括：本发明提供一种与药液接触时所得到的药液的残渣缺陷抑制性及桥接缺陷抑制性优异的部件。并且,提供一种容器、药液收容体、反应槽、蒸馏塔、过滤器单元、存储罐、管路及药液的制造方法。本发明的部件为与药液接触的部件,上述部件的表面由含有铬原子及铁原子的不锈钢构成,从上述部件的表面沿着深度方向至10nm,测量上述铬原子相对于上述铁原子的原子比时,在从上述部件的表面沿深度方向3nm以内显示上述原子比的最大值,上述最大值为0.5～3.0,上述部件的表面的表面平均粗糙度为10nm以下。(The invention provides a component which is excellent in residue defect suppression and bridging defect suppression of a chemical solution obtained when the component is brought into contact with the chemical solution. Also provided are a container, a chemical liquid container, a reaction tank, a distillation column, a filter unit, a storage tank, a pipeline, and a method for producing a chemical liquid. The member of the present invention is a member which comes into contact with a chemical solution, wherein the surface of the member is made of stainless steel containing chromium atoms and iron atoms, and when the atomic ratio of the chromium atoms to the iron atoms is measured from the surface of the member along the depth direction to 10nm, the maximum value of the atomic ratio is shown within 3nm in the depth direction from the surface of the member, the maximum value is 0.5 to 3.0, and the surface average roughness of the surface of the member is 10nm or less.)

1. A component which is in contact with a liquid medicine, wherein,

the surface of the member is made of stainless steel containing chromium atoms and iron atoms,

when the atomic ratio of the chromium atoms to the iron atoms is measured from the surface of the component along the depth direction to 10nm, a maximum value of the atomic ratio is shown within 3nm in the depth direction from the surface of the component,

the maximum value is 0.5 to 3.0,

the surface average roughness of the surface of the member is 10nm or less.

2. The component of claim 1, wherein,

the surface average roughness is 0.10 nm-10 nm.

3. The component of claim 1 or 2,

the atomic ratio of the chromium atoms to the iron atoms on the surface of the component is 1.1-2.5.

4. The component of any one of claims 1 to 3,

electropolishing the surface of the component.

5. The component of claim 4, wherein,

the surface of the component is subjected to a surface treatment other than the electrolytic polishing before the electrolytic polishing.

6. The component of claim 4 or 5,

after the electrolytic polishing, the surface of the member is also subjected to an acid treatment.

7. The member according to any one of claims 1 to 6, which is used for at least 1 selected from the group consisting of production, storage, transportation, and transfer of a chemical liquid for semiconductor manufacturing.

8. The component of claim 7, wherein,

the volume resistivity of the chemical solution is 500,000,000 Ω m or more.

9. A container for containing a medicinal liquid, wherein,

at least a part of the liquid-receiving portion of the solution contains the member according to any one of claims 1 to 8.

10. A chemical liquid container comprising the container according to claim 8 and a chemical liquid contained in the container.

11. The chemical liquid container according to claim 10,

the liquid medicine is a mixed solvent, and the mixed solvent contains 20-80% by mass of a Hansen solubility parameter relative to eicosene and has a distance of 3MPa relative to the total mass of the liquid medicine^0.5～20MPa^0.5And a distance of not less than 3MPa containing 20 to 80 mass% of the Hansen solubility parameter relative to eicosene based on the total mass of the chemical solution^0.5～20MPa^0.5The organic solvent of (1).

12. The chemical liquid container according to claim 10,

the liquid medicine contains a solvent selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl acetate, cyclohexanone, 4-methyl-2-pentanol, isopropanol, ethanol, acetone, propylene carbonate, gamma-butyrolactone, isoamyl acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethyl lactate, methyl methoxypropionate, cyclopentanone, diisoamyl ether, dimethyl sulfoxide, N-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, sulfolane, cycloheptanone, 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, isoamyl propionate, ethylcyclohexane, mesitylene, decane, 3, 7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, 2-octanol, Ethyl acetoacetate, dimethyl malonate, methyl pyruvate and dimethyl oxalate.

13. The medical fluid container according to any one of claims 10 to 12,

the volume resistivity of the chemical solution is 500,000,000 Ω m or more.

14. The chemical liquid container according to claim 10,

the liquid medicine is alkaline developing solution.

15. The medical fluid container according to any one of claims 10 to 14,

the chemical liquid contains a high-boiling-point organic component having a boiling point of 250 ℃ or higher in an amount of 0.1 to 100000 mass ppt relative to the mass of the chemical liquid.

16. The medical fluid container according to any one of claims 10 to 15,

and an inert gas is filled in the gap in the container.

17. A reaction vessel for reacting a raw material to obtain a chemical solution as a reactant, wherein,

at least a part of the liquid-receiving portion of the reaction tank includes the member according to any one of claims 1 to 8.

18. A distillation column for purifying a substance to be purified to obtain a chemical solution as a purified substance, wherein,

at least a portion of the liquid-receiving portion of the distillation column comprises the component of any one of claims 1 to 8.

19. A filter unit for purifying a substance to be purified to obtain a chemical solution as a purified substance,

at least a portion of the liquid-receiving portion of the filter unit comprises the member of any one of claims 1 to 8.

20. A storage tank for storing the liquid medicine, wherein,

at least a portion of the liquid receiving portion of the storage tank comprises the component of any one of claims 1 to 8.

21. A line for transferring the medical fluid, wherein,

at least a portion of the liquid-receiving portion of the pipeline comprises the component of any one of claims 1 to 8.

22. A method for producing a chemical solution, using a chemical solution production apparatus provided with at least 1 selected from the group consisting of the reaction tank according to claim 17, the distillation column according to claim 18, the filter unit according to claim 19, the tank according to claim 20, and the line according to claim 21.

23. The method for producing chemical liquid according to claim 22, wherein,

the chemical solution contains an organic solvent selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl methoxypropionate, cyclopentanone, cyclohexanone, gamma-butyrolactone, diisoamyl ether, butyl acetate, isoamyl acetate, isopropanol, 4-methyl-2-pentanol, dimethyl sulfoxide, N-methyl-2-pyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, propylene carbonate, sulfolane, cycloheptanone, 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, isoamyl propionate, ethylcyclohexane, mesitylene, decane, 3, 7-dimethyl-3-octanol, 2-ethyl-1-hexanol, N-butyl acetate, N-methyl-2-pyrrolidone, N-methyl-2-pentanol, N-methyl-2-methyl-pyrrolidone, N, 1-octanol, 2-octanol, ethyl acetoacetate, dimethyl malonate, methyl pyruvate and dimethyl oxalate.

24. The method for producing chemical liquid according to claim 23,

the volume resistivity of the chemical solution is 500,000,000 Ω m or more.

25. The method for producing chemical liquid according to claim 22, wherein,

the liquid medicine is alkaline developing solution.

Technical Field

The present invention relates to a member, a container, a chemical liquid container, a reaction tank, a distillation column, a filter unit, a storage tank, a pipeline, and a method for producing a chemical liquid.

Background

The semiconductor manufacturing process includes various processes such as a photolithography process, an etching process, an ion implantation process, and a lift-off process. However, after each process is completed or before the next process is continued, a process of performing treatment with a chemical solution is generally included.

In a semiconductor manufacturing process, since defects are generated due to a small amount of foreign matter or the like, the chemical solution is generally required to have characteristics of high purity and high cleanliness. For example, it is known that chemical solutions such as a pre-wet solution, a developing solution, and a rinse solution used in a photolithography process have a large influence on the performance of a pattern formed with impurities such as a trace amount of metal components.

The content of metal component impurities is further reduced by using a fluororesin material for the liquid-contacting portion, but when a solvent exhibiting high volume resistance is used, static electricity is generated due to flowing charge or the like, particularly when it exceeds 2kV, and there is a risk of damage to the liquid-contacting member and/or contamination of the liquid due to discharge depending on the method of use.

Patent document 1 discloses a high-purity chemical supply apparatus capable of maintaining a very small amount of particles in a high-purity chemical, the supply apparatus including a stainless steel container itself whose inner surface is electropolished.

Prior art documents

Patent document

Patent document 1: japanese patent laid-open publication No. 2004-233254

Disclosure of Invention

Technical problem to be solved by the invention

The present inventors have studied the chemical liquid contained in the container disclosed in patent document 1, and as a result, have found that there is room for improvement in the residue defect suppression property and the bridging defect suppression property of the chemical liquid after storage.

Accordingly, an object of the present invention is to provide a member having excellent residue defect suppression and bridging defect suppression of a chemical solution obtained when the member is brought into contact with the chemical solution.

Another object of the present invention is to provide a container, a chemical liquid container, a reaction tank, a distillation column, a filter unit, a storage tank, a pipeline, and a method for producing a chemical liquid.

Means for solving the technical problem

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following configuration.

[ 1] A member which is brought into contact with a liquid medicine, wherein,

the surface of the member is made of stainless steel containing chromium atoms and iron atoms,

when the atomic ratio of the chromium atom to the iron atom is measured from the surface of the member in the depth direction to 10nm, the maximum value of the atomic ratio is shown within 3nm in the depth direction from the surface of the member,

the maximum value is 0.5 to 3.0,

the surface of the member has a surface average roughness of 10nm or less.

[ 2] the member according to [ 1], wherein,

the surface average roughness is 0.10 to 10 nm.

[ 3] the member according to [ 1] or [ 2], wherein,

the atomic ratio of the chromium atoms to the iron atoms on the surface of the member is 1.1 to 2.5.

[ 4] the member according to any one of [ 1] to [ 3], wherein,

the surface of the above-mentioned member was subjected to electrolytic polishing.

[ 5] the member according to [ 4], wherein,

before the above electrolytic polishing, the surface of the above member is subjected to a surface treatment other than the above electrolytic polishing.

[ 6] the member according to [ 4] or [ 5], wherein,

after the above electrolytic polishing, the surface of the above member is also subjected to an acid treatment.

[ 7] the member according to any one of [ 1] to [ 6], which is used for at least 1 selected from the group consisting of production, storage, transportation, and transfer of a chemical liquid for semiconductor manufacturing.

[ 8] the member according to [ 7], wherein,

the volume resistivity of the chemical solution is 500,000,000 Ω m or more.

[ 9] A container for containing a liquid medicine, wherein,

at least a part of the liquid-receiving portion of the solution contains the member according to any one of [ 1] to [ 8 ].

[ 10] A chemical liquid container comprising the container according to [ 8] and a chemical liquid contained in the container.

[ 11] the chemical solution containing body according to [ 10], wherein,

the liquid medicine is a mixed solvent, and the mixed solvent contains 20-80% by mass of the total mass of the liquid medicine, and the distance of the Hansen solubility parameter relative to the eicosene is 3-20 MPa^0.5And 2 is contained in the total amount of the chemical solution0 to 80 mass% of a distance of not 3 to 20MPa relative to the Hansen solubility parameter of eicosene^0.5The organic solvent of (1).

[ 12] the chemical solution containing body according to [ 10], wherein,

the medicinal liquid contains one or more compounds selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl acetate, cyclohexanone, 4-methyl-2-pentanol, isopropanol, ethanol, acetone, propylene carbonate, gamma-butyrolactone, isoamyl acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethyl lactate, methyl methoxypropionate, cyclopentanone, diisoamyl ether, dimethyl sulfoxide, N-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, sulfolane, cycloheptanone and 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, isoamyl propionate, ethylcyclohexane, mesitylene, decane, 3, 7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, 2-octanol, Ethyl acetoacetate, dimethyl malonate, methyl pyruvate and dimethyl oxalate.

[ 13] the chemical solution containing body according to any one of [ 10] to [ 12], wherein,

the volume resistivity of the chemical solution is 500,000,000 Ω m or more.

[ 14] the chemical solution containing body according to [ 10], wherein,

the liquid medicine is alkaline developing solution.

[ 15] the chemical solution containing body according to any one of [ 10] to [ 14], wherein,

the chemical solution contains 0.1 to 100000 mass ppt of an organic component having a boiling point of 250 ℃ or higher based on the mass of the chemical solution.

[ 16 ] the chemical solution containing body according to any one of [ 10] to [ 15], wherein,

an inert gas is filled in the space in the container.

[ 17 ] A reaction vessel for reacting a raw material to obtain a chemical solution as a reactant, wherein,

at least a part of the liquid-receiving portion of the reaction vessel contains the member according to any one of [ 1] to [ 8 ].

[ 18 ] A distillation column for purifying a purified product to obtain a chemical solution as a purified product, wherein,

at least a part of the liquid-receiving portion of the distillation column contains the member according to any one of [ 1] to [ 8 ].

[ 19 ] A filter unit for purifying a purified product to obtain a chemical solution as a purified product, wherein,

at least a part of the liquid receiving portion of the filter unit includes any one of the members [ 1] to [ 8 ].

[ 20 ] A storage tank for storing a raw material for obtaining a chemical solution as a reactant by performing a reaction or a purified product for obtaining a chemical solution as a purified product by performing purification, wherein,

at least a part of the liquid receiving portion of the tank may include any one of the components [ 1] to [ 8 ].

[ 21 ] A line for transferring the chemical liquid, wherein,

at least a part of the liquid-receiving portion of the pipe line includes any one of the members [ 1] to [ 8 ].

[ 22 ] A chemical liquid production method for producing a chemical liquid using a chemical liquid production apparatus selected from at least 1 of the group consisting of the reaction tank [ 17 ], the distillation column [ 18 ], the filter unit [ 19 ], the tank [ 20 ] and the pipeline [ 21 ].

[ 23 ] the method for producing a chemical liquid according to [ 22 ], wherein,

the chemical solution contains an organic solvent, and the organic solvent contains a solvent selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl methoxypropionate, cyclopentanone, cyclohexanone, gamma-butyrolactone, diisoamyl ether, butyl acetate, isoamyl acetate, isopropanol, 4-methyl-2-pentanol, dimethyl sulfoxide, N-methyl-2-pyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, propylene carbonate, sulfolane, cycloheptanone, 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, isoamyl propionate, ethylcyclohexane, mesitylene, decane, 3, 7-dimethyl-3-octanol, 2-ethyl-1-hexanol, N-butyl acetate, N-methyl-2-pyrrolidone, N-methyl-2-pentanol, N-methyl-2-pentanol, 1-octanol, 2-octanol, ethyl acetoacetate, dimethyl malonate, methyl pyruvate and dimethyl oxalate.

[ 24 ] the method for producing a chemical liquid according to [ 23 ], wherein,

the volume resistivity of the chemical solution is 500,000,000 Ω m or more.

[ 25 ] the method for producing a chemical liquid according to [ 22 ], wherein,

the liquid medicine is alkaline developing solution.

Effects of the invention

According to the present invention, a member having excellent residue defect suppression and bridging defect suppression of a chemical solution obtained when the member is brought into contact with the chemical solution can be provided.

The present invention also provides a container, a chemical liquid container, a reaction tank, a distillation column, a filter unit, a storage tank, a pipeline, and a method for producing a chemical liquid.

Drawings

FIG. 1 is a schematic view of a lidded container containing a container and lid of an embodiment of the present invention.

Fig. 2 is a schematic diagram of a manufacturing apparatus according to an embodiment of the method for manufacturing a chemical solution of the present invention.

Fig. 3 is a perspective view of a typical filter provided in the filter unit, with a part removed.

Fig. 4 is a perspective view of a housing provided in the filter unit.

Fig. 5 is a partial sectional view of a housing provided in the filter unit.

Fig. 6 is a schematic diagram of a manufacturing apparatus according to an embodiment of the method for manufacturing a chemical solution of the present invention.

Fig. 7 is a schematic diagram of a manufacturing apparatus according to an embodiment of the method for manufacturing a chemical solution of the present invention.

Detailed Description

The present invention will be described in detail below.

The following description of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

In the present specification, the numerical range expressed by the term "to" means a range including numerical values before and after the term "to" as a lower limit value and an upper limit value.

In the present invention, "ppm" means "parts-per-million (10)^-6) Parts per million and ppb refers to parts-per-billion (10)^-9) Parts per billion and ppt refer to parts-per-trillion (10)^-12) One in one part, the term "ppq" refers to "parts-per-quatrilion (10)^-15) One giga ".

In the labeling of the group (atomic group) in the present invention, the label not labeled with substituted or unsubstituted labels includes not only a group having no substituent but also a group having a substituent within a range not impairing the effect of the present invention. For example, "a hydrocarbon group" includes not only a hydrocarbon group having no substituent (unsubstituted hydrocarbon group) but also a hydrocarbon group having a substituent (substituted hydrocarbon group). The same applies to each compound.

The term "radiation" in the present invention refers to, for example, Extreme Ultraviolet (EUV), X-ray, electron beam, or the like. In the present invention, light means actinic rays or radiation. The "exposure" in the present invention includes, unless otherwise specified, not only exposure using extreme ultraviolet rays, X-rays, EUV, or the like, but also drawing using a particle beam such as an electron beam or an ion beam.

[ Components ]

The member of the present invention is a member that comes into contact with the chemical solution.

The surface of the member is made of stainless steel containing chromium atoms and iron atoms.

When the atomic ratio of chromium atoms to iron atoms is measured from the surface of the component along the depth direction to 10nm, the maximum value of the atomic ratio (Cr/Fe ratio) is within 3nm along the depth direction from the surface of the component, and the maximum value is 0.5-3.0.

The surface of the member has a surface average roughness of 10nm or less.

Although the mechanism for solving the problems of the present invention using the member having such a structure is not clear, the present inventors believe that, in order to control the relationship between the profile of the Cr/Fe ratio in the depth direction of stainless steel and the roughness of the surface within a predetermined range, the transfer of metal components from stainless steel to the chemical solution or the like can be suppressed in a synergistic effect, and the residue defect suppression property and the bridging defect suppression property of the obtained chemical solution can be improved.

The residue defect refers to, for example, a particle defect when a chemical solution is used as a pre-wetting liquid or a rinse liquid, and the bridging defect refers to, for example, a cross-linking defect between patterns when a chemical solution is applied to pattern formation.

Hereinafter, the case where at least one of the residue defect suppression property and the bridge defect suppression property of the chemical solution is good is also referred to as "excellent effect of the present invention" or the like.

Further, according to the member of the present invention, the liquid-receiving member portion formed using a conventional fluororesin material can be replaced with a stainless steel member, and the risk of damage to the liquid-receiving member and/or contamination of the liquid due to static electricity can be reduced.

[ stainless steel ]

The surface of the member of the present invention is made of stainless steel containing chromium atoms and iron atoms.

The surface of the member of the present invention may be made of the above stainless steel, the entire member may be made of the above stainless steel, or the member may have a base material made of a material other than stainless steel and a coating layer made of the above stainless steel disposed on the base material. That is, the member has a base material other than stainless steel and a coating layer made of the stainless steel disposed on the base material, and the coating layer also satisfies the requirements described below.

< Cr/Fe ratio >

The stainless steel contains chromium atoms and iron atoms.

When the atomic ratio of chromium atoms to iron atoms (Cr/Fe ratio) was measured from the surface of the member to 10nm in the depth direction, the maximum value of the atomic ratio was exhibited within 3nm in the depth direction from the surface of the member.

When the depth from the surface of the component at which the Cr/Fe ratio is the maximum is defined as a specific depth, it can be interpreted that the specific depth is within 3nm in the depth direction from the surface of the component.

The maximum Cr/Fe ratio of the stainless steel (in other words, the Cr/Fe ratio at a specific depth) is 0.5 to 3.0, preferably 0.7 to 2.8, and more preferably 1.1 to 2.5.

The specific depth may be within 3nm in the depth direction from the surface of the member in the liquid-contacting portion, and the surface (depth 0nm) of the member may be the specific depth.

The Cr/Fe ratio of the surface (depth 0nm) of the member is preferably 0.4 to 3.0, more preferably 0.7 to 2.8, and most preferably 1.1 to 2.5.

Preferably, the Cr/Fe ratio of the stainless steel is gradually decreased as the depth from the surface of the member becomes deeper than a specific depth.

The Cr/Fe ratio from the surface of the member to the position of 10nm depth is not particularly limited, but is preferably 0.3 to 0.6, more preferably 0.3 to 0.5.

The value of the Cr/Fe ratio in the depth direction from the surface of the member to a depth of 10nm or more is not particularly limited, but is preferably substantially constant. The term "substantially constant" means that the absolute value of the rate of change of the Cr/Fe ratio at a 10nm position is within 5%. The above change rate represents (Cr/Fe ratio at 10 nm-Cr/Fe ratio at a predetermined position)/(Cr/Fe ratio at 10 nm). times.100.

In the present specification, the Cr/Fe ratio at each depth was measured as described below.

First, the surface of the member was subjected to Ar gas etching for 60 minutes. The average etching rate is calculated from the etched depth (etching depth), and the etching treatment time for etching to a desired depth is determined. In addition, at this time, the etching depth was measured using an Atomic Force Microscope (AFM).

Etching is performed from the surface of the member for 1nm each time based on the determined etching treatment time, and measurements are performed at each depth using ESCA (Electron Spectroscopy for Chemical Analysis), for example, ESCA-3400 manufactured by Shimadzu Corporation) to calculate the atomic% of each element from the peak intensity and find the Cr/Fe ratio.

The Cr/Fe ratio of the surface of the member was determined by measurement using ESCA without performing the etching.

< surface average roughness >

The surface average roughness (Ra) of the surface of the member is 10nm or less, preferably 0.10 to 10nm, more preferably 0.20 to 5 nm.

When the surface average roughness is 10nm or less, the microscopic contact area with the chemical solution or the like on the surface of the component can be reduced, and the influence on the impurity content of the chemical solution can be suppressed. When the surface average roughness is 0.10nm or more, metal fine particles generated in the process of smoothing the surface average roughness are easily prevented from being mixed into the chemical solution, and the effect of the present invention is more excellent.

In the present invention, the surface average roughness of the stainless steel can be measured by an Atomic Force Microscope (AFM).

< surface treatment >

The surface of the member is preferably subjected to surface treatment.

The surface treatment is preferably a surface treatment based on electrolytic polishing.

As the treatment liquid (electrolytic solution) in the electrolytic polishing, a mixed solution of phosphoric acid and sulfuric acid is preferable, and the mixing ratio thereof is, for example, preferably 85 mass% phosphoric acid to 98 mass% sulfuric acid of 4: 3 (volume ratio).

The liquid temperature during electrolytic polishing is preferably 30 to 60 ℃, more preferably 40 to 50 ℃.

The current density during electrolytic polishing is preferably 10-20A/dm²。

The time for the electrolytic polishing is preferably 10 to 120 minutes, more preferably 30 to 60 minutes.

Before and after the electrolytic polishing, the surface of the member is preferably subjected to a pretreatment (polishing, magnetofluid polishing, or the like) and/or a post-treatment (annealing, acid treatment, or the like), and more preferably at least the pretreatment is performed.

As the pretreatment, polishing is preferable.

The size of the abrasive grains used in the polishing treatment is preferably #400 or less, more preferably #1000 to #400, and still more preferably #600 to # 400.

Examples of the treatment liquid used in the acid treatment include acids such as sulfuric acid, phosphoric acid, hydrochloric acid, fluoric acid, and mixed acids containing one or more of these acids, and diluted aqueous solutions of the acids. The acid treatment may be, for example, a method of bringing a treatment liquid into contact with a surface to be treated, and more specifically, may be a method of immersing a treatment object in a treatment layer filled with the treatment liquid. At this time, circulation, heating, and the like of the treatment liquid may be appropriately performed.

The acid treatment may be performed by applying a slurry-like treatment liquid to the surface to be treated.

The stainless steel (stainless steel) is not particularly limited as long as the surface of the member satisfies the predetermined requirements, and known stainless steel can be used. Among these, an alloy containing 8 mass% or more of nickel is preferable, and an austenitic stainless steel containing 8 mass% or more of nickel is more preferable. Examples of austenitic Stainless Steel include SUS (Steel Use Stainless) 304 (with a Ni content of 8 mass% and a Cr content of 18 mass%), SUS304L (with a Ni content of 9 mass% and a Cr content of 18 mass%), SUS316 (with a Ni content of 10 mass% and a Cr content of 16 mass%), and SUS316L (with a Ni content of 12 mass% and a Cr content of 16 mass%).

[ use ]

The member of the present invention is preferably used for at least 1 selected from the group consisting of production, storage, transportation, and transfer of a chemical liquid (preferably, a chemical liquid for semiconductor production).

Specific applications include containers for storing chemical solutions, apparatuses for producing chemical solutions (such as purification apparatuses and reaction apparatuses), and pipelines.

The member of the present invention is also preferably used in the case where the liquid medicine to be brought into contact (manufacture, storage, transportation and/or transfer, etc.) has a volume resistivity of 500,000,000 Ω m or more.

In particular, when the chemical liquid contained in the chemical liquid container of the present invention described later or the chemical liquid in the method for producing the chemical liquid of the present invention described later has a volume resistivity of 500,000,000 Ω m or more, the member of the present invention (the container of the present invention, the reaction tank of the present invention, the distillation column of the present invention, the filter unit of the present invention, the storage tank of the present invention, the pipeline of the present invention, or the like) can be preferably used.

When the chemical liquid having such a high volume resistivity is brought into contact with a member made of a fluororesin material, when there is a risk of damage to the liquid-receiving member and/or contamination of the liquid due to discharge, the surface of the member of the present invention is made of stainless steel, so that electrostatic charge is not generated and the above-mentioned risk can be reduced. Further, it is considered that the transfer of metal components from a metal material (stainless steel) can be suppressed in the member of the present invention, and contamination from a chemical liquid other than the metal material can be reduced.

The volume resistivity of the liquid medicine can be measured using, for example, a volume resistivity meter SME-8310 or a super insulation meter SM-8220 manufactured by HIOKI e.e. The measurement temperature was set to 23 ℃.

Further, if the charge potential of the chemical solution in contact with the member of the present invention is within-2 kV to 2kV, it can be determined that the above-mentioned risk (damage of the liquid contact member and/or contamination of the liquid accompanying the discharge) is small.

The measurement of the static electricity (charge potential) of the chemical solution can be performed, for example, as described below. That is, the charge potential on the outer side near the center of the tube (1.5m portion) was measured by cutting a PFA-HG tube (inner diameter: 4.35mm, outer diameter: 6.35mm) manufactured by NICIAS Corporation into a length of 3m, passing a liquid to be measured (drug liquid) at a flow rate of 0.5m/sec, and using a digital electrostatic potential measuring instrument KSD-3000 manufactured by KASUGA DENKI, Inc. The measurement temperature was set to 23 ℃.

[ Container ]

The container of the embodiment of the present invention may be formed using the above-described component of the present invention (hereinafter, also referred to as "specified component").

More specifically, the container according to the embodiment of the present invention is a container for containing a chemical liquid, and at least a part of the liquid-receiving portion of the container is constituted by a predetermined member.

In other words, the container of the present invention is a container for containing a chemical liquid, wherein at least a part of a liquid contact portion of the container is made of stainless steel containing chromium atoms and iron atoms, and when an atomic ratio of chromium atoms to iron atoms is measured from a surface of the container in the liquid contact portion along a depth direction to 10nm, a maximum value of the atomic ratio is shown within 3nm in the depth direction from the surface of the container, the maximum value of the atomic ratio is 0.5 to 3.0, and a surface average roughness of the surface of the container in the liquid contact portion is 10nm or less.

The following is a detailed description with reference to the drawings.

A schematic view of a lidded container containing a container and a lid of an embodiment of the present invention is shown in fig. 1.

The lidded container 10 includes a hollow container 11 and a lid 12, and can be fitted to each other by a male screw, not shown, provided on the outside of a mouth portion 13 of the container and a female screw, not shown, provided on the inside of a side portion 14 of the lid 12. The fitted container 11 and lid 12 form a cavity L in the capped container 10, and a liquid (e.g., a chemical liquid for semiconductor manufacturing) can be contained in the cavity L.

The liquid receiving portion of the capped container 10 includes a predetermined member.

That is, the inner wall surface 15 of the liquid-contacting portion of the lidded container 10 is made of stainless steel containing chromium atoms and iron atoms.

The inner wall surface 15 has the specific depth within 3nm from the surface, the Cr/Fe ratio is 0.5-3.0, and the surface average roughness is 10nm or less.

In fig. 1, the entire surface of the inner wall surface 15 of the lidded container 10 is formed of the predetermined member, but the container according to the embodiment of the present invention is not limited to the above, and at least a part of the liquid contact portion of the inner wall surface may be formed of the predetermined member. More specifically, it is preferable that 70% or more of the entire surface area of the liquid-contacting portion contain the predetermined member, more preferably 80% or more of the entire surface area of the liquid-contacting portion contain the predetermined member, still more preferably 90% or more of the entire surface area of the liquid-contacting portion contain the predetermined member, and particularly preferably the entire surface of the liquid-contacting portion contains the predetermined member.

In the above container, when the chemical liquid is stored inside, the liquid contact portion (which is a surface that is in contact with the object and is likely to come into contact with the object even if not actually) includes a predetermined member (made of a member), and therefore, even if the chemical liquid is stored, the impurity content of the chemical liquid is less likely to be affected, and the effect of the present invention is excellent.

In the above-described lidded container 10, the inner wall surface 15 is formed of a predetermined member, but the outer wall surface 16 may be formed of a predetermined member.

[ chemical solution Container ]

The chemical liquid container according to the embodiment of the present invention includes the container described above and the chemical liquid contained in the container. In the chemical liquid container according to the embodiment of the present invention, since at least a part of the liquid-receiving portion of the container includes the predetermined member, even when the chemical liquid container is stored for a long period of time, the impurity content of the stored chemical liquid is less likely to be affected, and the effect of the present invention is excellent.

< medicinal liquid >

The chemical solution is preferably used as a chemical solution for semiconductor production. Moreover, a chemical solution in which metal impurities and organic impurities are reduced is preferable. The chemical liquid is not limited in kind, but may be a high-purity liquid among a polishing material used for producing a semiconductor, a liquid containing a resist composition, a pre-wetting liquid, a developing liquid, a rinse liquid, a stripping liquid, and the like, and a high-purity liquid among a developing liquid and a rinse liquid, such as a polyimide, a resist for a sensor, a resist for a lens, and the like, in the course of use other than production of a semiconductor.

In addition, in 1 of the preferred embodiments, the chemical solution contains an organic solvent.

Hereinafter, a description will be given of a distinction between an organic solvent-based chemical liquid in which the content of an organic solvent (the total content of a plurality of organic solvents when included) exceeds 50 mass% with respect to the total mass of the solvents included in the chemical liquid, and an aqueous chemical liquid in which the content of water exceeds 50 mass% with respect to the total mass of the solvents included in the chemical liquid.

(organic solvent-based drug solution)

The organic solvent-based chemical liquid contains a solvent, and the content of the organic solvent is more than 50% by mass relative to the total mass of the solvent contained in the chemical liquid.

The organic solvent-based chemical liquid contains an organic solvent. The content of the organic solvent in the organic solvent-based chemical liquid is not particularly limited, but is preferably 99.0 mass% or more based on the total mass of the organic solvent-based chemical liquid. The upper limit is not particularly limited, but is preferably 99.99999% by mass or less.

The organic solvent may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When 2 or more organic solvents are used in combination, the total content is preferably within the above range.

In the present specification, the organic solvent refers to a liquid organic compound containing 1 component at a content of more than 10000 ppm by mass relative to the total mass of the chemical solution. That is, in the present specification, the liquid organic compound contained in an amount exceeding 10000 ppm by mass relative to the total mass of the chemical solution belongs to the organic solvent.

In the present specification, the term "liquid" means a liquid at 25 ℃ under atmospheric pressure.

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

Further, as the organic solvent, for example, the organic solvents described in Japanese patent application laid-open Nos. 2016-057614, 2014-219664, 2016-138219, and 2015-135379 may be used.

The organic solvent is also excellentFor example, the distance between the Hansen solubility parameter and the eicosene is 3-20 MPa^0.5(more preferably 5 to 20 MPa)^0.5)。

In the case of using 2 or more organic solvents, it is preferable that at least 1 satisfies the above range of hansen solubility parameters.

When 2 or more organic solvents are used, it is preferable that the weighted average of the hansen solubility parameters based on the molar ratio of the contents of the respective organic solvents satisfies the range of the hansen solubility parameters.

For example, the organic solvent in the chemical solution is preferably only an organic solvent that substantially satisfies the range of the hansen solubility parameter. The organic solvent in the chemical solution is only an organic solvent that substantially satisfies the range of the hansen solubility parameter, which means that the content of the organic solvent that satisfies the range of the hansen solubility parameter is 99 mass% or more (preferably 99.9 mass% or more) with respect to the total mass of the organic solvent.

For example, the organic solvent preferably contains a mixed solvent of an organic solvent satisfying the range of the hansen solubility parameter and an organic solvent not satisfying the range of the hansen solubility parameter.

In this case, the chemical solution (mixed solvent) preferably contains 20 to 80 mass% (preferably 30 to 70 mass%) of the organic solvent satisfying the hansen solubility parameter with respect to the total mass of the chemical solution, and preferably contains 20 to 80 mass% (preferably 30 to 70 mass%) of the organic solvent not satisfying the hansen solubility parameter with respect to the total mass of the chemical solution.

When the content of the organic solvent satisfying the range of the hansen solubility parameter and the content of the organic solvent failing to satisfy the range of the hansen solubility parameter are respectively within predetermined ranges, it is considered that the affinity of the liquid medicine for the metal-based raw material and the organic-based raw material can be adjusted to an appropriate range as compared with the case where the content of the organic solvent failing to satisfy the range of the hansen solubility parameter is excessive or too small (for example, 1% by mass or more and less than 20% by mass or more and more than 80% by mass with respect to the total mass of the liquid medicine (mixed solvent)), and the effect of the present invention is more excellent.

In this case, the total content of the organic solvent satisfying the range of the hansen solubility parameter and the organic solvent failing to satisfy the range of the hansen solubility parameter is preferably 99.0 mass% or more with respect to the total mass of the chemical solution. The upper limit is not particularly limited, but is preferably 99.99999% by mass or less.

Further, the distance between the hansen solubility parameter of eicosene in the organic solvent not satisfying the range of the hansen solubility parameter is OMPa^0.5Above and less than 3MPa^0.5(preferably in excess of OMPa)^0.5And less than 3MPa^0.5) Or more than 20MPa^0.5(preferably more than 20 MPa)^0.5And 50MPa^0.5Below).

In the present specification, the Hansen Solubility parameter refers to "Hansen Solubility Parameters: hansen solubility parameters described in A Users Handbook, Second Edition (pp. 1-310, CRC Press, 2007), and the like. That is, it is considered that, in the hansen solubility parameter, solubility is expressed by multidimensional vectors (dispersion term (δ d), dipole term (δ p), and hydrogen bond term (δ h)), and these 3 parameters are coordinates of points in a three-dimensional space called hansen space.

The distance of hansen solubility parameters is the distance in hansen space of 2 compounds, and the distance of hansen solubility parameters is obtained by the following formula.

(Ra)²＝4(δd2-δd1)²+(δp2-δp1)²+(δh2-δh1)²

Ra: distance of Hansen solubility parameter of compound No. 1 and Compound No. 2 (unit: MPa)^0.5)

δ d 1: dispersion term (unit: MPa) of Compound No. 1^0.5)

δ d 2: dispersion term (unit: MPa) of Compound No. 2^0.5)

δ p 1: dipolar term of Compound No. 1 (unit: MPa)^0.5)

δ p 2: dipole term (unit: MPa) of the 2 nd compound^0.5)

δ h 1: hydrogen bonding term of Compound No. 1 (unit: MPa)^0.5)

δ h 2: hydrogen bonding term of the 2 nd compound (unit: MPa)^0.5)

In the present specification, the Hansen Solubility Parameter of a compound is specifically calculated using HSPiP (Hansen Solubility Parameter in Practice).

The organic solvent preferably contains a solvent selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl acetate, cyclohexanone, 4-methyl-2-pentanol, isopropanol, ethanol, acetone, propylene carbonate, γ -butyrolactone, isoamyl acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethyl lactate, methyl methoxypropionate, cyclopentanone, diisoamyl ether, dimethyl sulfoxide, N-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, sulfolane, cycloheptanone, 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, isoamyl propionate, ethylcyclohexane, mesitylene, decane, 3, 7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, and the like, 2-octanol, ethyl acetoacetate, dimethyl malonate, methyl pyruvate and dimethyl oxalate.

In addition, the type and content of the organic solvent in the liquid medicine can be measured by using a gas chromatograph-mass spectrometer.

[ Metal component ]

The organic solvent-based chemical liquid may contain a metal component.

In the present invention, the metal component is, for example, metal particles.

Examples of the metal element in the metal component include Al (aluminum), B (boron), Ba (barium), Ca (calcium), Cd (cadmium), Co (cobalt), Cr (chromium), Cu (copper), Fe (iron), K (potassium), Li (lithium), Mg (magnesium), Mn (manganese), Mo (molybdenum), Na (sodium), Ni (nickel), P (phosphorus), Pb (lead), Sb (antimony), Si (silicon), Ti (titanium), V (vanadium), and Zn (zinc).

Among them, the metal element in the metal component is preferably 1 or more selected from the group consisting of Ni, Fe, and Cr. Hereinafter, these metal elements are also referred to as specific metal elements, in particular. The metal component and the metal particles containing the specific metal element are also referred to as a specific metal component and a specific metal particle, respectively.

The metal particles may be a single body or an alloy, may be an oxide, a nitride, an oxynitride, or another metal compound, or may be present in a form in which a metal (including a metal compound) is associated with an organic substance. The valence of the metal is not limited.

The metal component may be a metal component inevitably contained in the chemical liquid, may be a metal component inevitably contained in the processing liquid at the time of production, storage, and/or transfer, and may be intentionally added.

When the predetermined member is used in the liquid contact portion, the change in the content of the metal component (particularly, the specific metal particles) in the chemical liquid can be suppressed, and the obtained residue defect suppressing property and bridging defect suppressing property are excellent.

When the chemical solution contains a metal component (preferably a specific metal component), the content thereof is, for example, preferably 0.1 to 100 mass ppt, more preferably 0.1 to 10 mass ppt, based on the total mass of the chemical solution.

When the chemical solution contains metal particles (preferably, specific metal particles), the content thereof is preferably 0.001 to 100 mass ppt, more preferably 0.001 to 10 mass ppt, based on the total mass of the chemical solution.

Further, the kind and content of the metal particles (specific metal particles) in the chemical solution can be measured by a Single Nano Particle Inductively Coupled Plasma Mass Spectrometry (SP-ICP-MS method).

Among them, the SP-ICP-MS method uses the same apparatus as the general ICP-MS method (inductively coupled plasma mass spectrometry), and only data analysis is different. Data analysis by the SP-ICP-MS method can be performed by commercially available software.

In the ICP-MS method, the content of a metal component to be measured is measured regardless of the existence mode thereof.

As an apparatus for the SP-ICP-MS method, for example, Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, option #200, for semiconductor analysis) was used, and the measurement was carried out by the method described in the examples. In addition to the above, other than NexION350S manufactured by PerkinElmer co., ltd., Agilent Technologies Japan, Ltd, and 8900 can be used.

Other ingredients

The chemical solution may contain other components than those described above. Examples of the other components include a resin, an organic substance other than the resin, and water.

Resin (A)

The chemical solution may contain a resin.

The chemical solution may further contain a resin. The resin P is more preferably a resin P containing a group which is decomposed by the action of an acid to generate a polar group.

The resin P is more preferably a resin whose solubility in a developer mainly composed of an organic solvent is reduced by the action of an acid, that is, a resin containing a repeating unit represented by formula (AI) described later. The resin containing a repeating unit represented by formula (AI) described later contains a group that is decomposed by the action of an acid to generate an alkali-soluble group (hereinafter, also referred to as an "acid-decomposable group").

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

In the acid-decomposable group, the polar group is protected by a group which leaves under the action of an acid (acid leaving group). As the acid leaving group, for example, there may be mentioned-C (R)₃₆)(R₃₇)(R₃₈)、-C(R₃₆)(R₃₇)(OR₃₉) and-C (R)₀₁)(R₀₂)(OR₃₉) And the like.

In the formula, R₃₆～R₃₉Each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R₃₆And R₃₇May be bonded to each other to form a ring.

R₀₁And R₀₂Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

Hereinafter, the resin P whose solubility in a developer mainly composed of an organic solvent is reduced by the action of an acid will be described in detail.

Formula (AI): repeating unit containing acid decomposable group

The resin P contains a repeating unit represented by the formula (AI).

[ chemical formula 1]

In the formula (AI), the reaction mixture is,

Xa₁represents a hydrogen atom or an alkyl group which may have a substituent.

T represents a single bond or a 2-valent linking group.

Ra₁～Ra₃Each independently represents an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic).

Ra₁～Ra₃2 of which may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

As a result of Xa₁Examples of the alkyl group which may have a substituent include a methyl group and-CH₂-R₁₁The group shown. R₁₁Represents a halogen atom (e.g., fluorine atom), a hydroxyl group or a 1-valent organic group.

Xa₁Preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

Examples of the linking group having a valence of 2 in T include an alkylene group, a-COO-Rt-group, and a-O-Rt-group. Wherein Rt represents an alkylene group or a cycloalkylene group.

T is preferably a single bond or a-COO-Rt-group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably-CH₂-radical, - (CH)₂)₂-radical or- (CH)₂)₃-a radical.

As Ra₁～Ra₃The alkyl group of (3) is preferably an alkyl group having 1 to 4 carbon atoms.

As Ra₁～Ra₃The cycloalkyl group of (3) is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a norbornyl, tetracyclodecyl or tetracyclododecyl groupOr polycyclic cycloalkyl groups such as adamantyl groups.

As Ra₁～Ra₃The cycloalkyl group in which 2 of them are bonded is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, or an adamantyl group. More preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

With respect to Ra₁～Ra₃The cycloalkyl group in which 2 of the above-mentioned cycloalkyl groups are bonded may be substituted with a heteroatom such as an oxygen atom or a heteroatom-containing group such as a carbonyl group, for example, 1 of methylene groups constituting the ring.

The repeating unit represented by the formula (AI) is preferably Ra, for example₁Is methyl or ethyl, and Ra₂And Ra₃Bonded to form the form of the cycloalkyl group.

The above groups may have a substituent, and examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms), and the number of carbon atoms is preferably 8 or less.

The content of the repeating unit represented by the formula (AI) is preferably 20 to 90 mol%, more preferably 25 to 85 mol%, and further preferably 30 to 80 mol% with respect to all repeating units in the resin P.

Repeating units containing a lactone structure

The resin P preferably contains a repeating unit Q having a lactone structure.

The repeating unit Q having a lactone structure preferably has a lactone structure in a side chain, and more preferably a repeating unit derived from a (meth) acrylic acid derivative monomer.

The lactone structure-containing repeating unit Q may be used alone in 1 kind or in combination of 2 or more kinds, but it is preferable to use one kind alone in 1 kind.

The content of the repeating unit Q having a lactone structure is preferably 3 to 80 mol%, more preferably 3 to 60 mol%, based on all repeating units in the resin P.

The lactone structure is preferably a 5-to 7-membered ring lactone structure, and more preferably a structure in which other ring structures are condensed in a manner to form a bicyclic structure or a spiro structure in the 5-to 7-membered ring lactone structure.

The lactone structure preferably contains a repeating unit having a lactone structure represented by any one of the following formulae (LC1-1) to (LC 1-17). The lactone structure is preferably a lactone structure represented by formula (LCI-1), formula (LCl-4), formula (LC1-5) or formula (LCl-8), more preferably a lactone structure represented by formula (LCl-4).

[ chemical formula 2]

The lactone moiety may have a substituent (Rb)₂). As preferred substituent (Rb)₂) Examples thereof include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, an acid-decomposable group and the like. n is₂Represents an integer of 0 to 4. When n is₂When it is 2 or more, a plurality of substituents (Rb)₂) May be the same or different, and a plurality of substituents (Rb) are present₂) May be bonded to each other to form a ring.

Repeating units containing phenolic hydroxyl groups

The resin P may contain a repeating unit having a phenolic hydroxyl group.

Examples of the repeating unit containing a phenolic hydroxyl group include a repeating unit represented by the following general formula (I).

[ chemical formula 3]

In the formula (I), the compound is shown in the specification,

R₄₁、R₄₂and R₄₃Each independently represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Wherein R is₄₂May be reacted with Ar₄Bonded to form a ring, in which case R₄₂Represents a single bond orAn alkyl group.

X₄Represents a single bond, -COO-or-CONR₆₄-，R₆₄Represents a hydrogen atom or an alkyl group.

L₄Represents a single bond or an alkylene group.

Ar₄An aromatic ring group having a (n +1) valence, when substituted with R₄₂And (n +2) -valent aromatic ring groups when bonded to form a ring.

n represents an integer of 1 to 5.

As R in the general formula (I)₄₁、R₄₂And R₄₃The alkyl group (b) is preferably an alkyl group having not more than 20 carbon atoms such as a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group, which may have a substituent, more preferably an alkyl group having not more than 8 carbon atoms, and still more preferably an alkyl group having not more than 3 carbon atoms.

As R in the general formula (I)₄₁、R₄₂And R₄₃The cycloalkyl group of (b) may be of a monocyclic type or of a polycyclic type. As the cycloalkyl group, preferred is a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.

As R in the general formula (I)₄₁、R₄₂And R₄₃Examples of the halogen atom of (2) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

As R in the general formula (I)₄₁、R₄₂And R₄₃The alkyl group contained in the alkoxycarbonyl group of (1) is preferably the same as the above-mentioned R₄₁、R₄₂And R₄₃The alkyl groups in (1) are the same groups.

Examples of the substituent in each of the above groups include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, an urea group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group, and the number of carbon atoms in the substituent is preferably 8 or less.

Ar₄Represents an (n +1) -valent aromatic ring group. When n is 1, the 2-valent aromatic ring group may have a substituent, and examples thereof include phenylene, tolylene,An arylene group having 6 to 18 carbon atoms such as naphthylene group and anthracenylene group, and an aromatic ring group containing a heterocycle such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, or thiazole.

Specific examples of the (n +1) -valent aromatic ring group in which n is an integer of 2 or more include groups obtained by removing (n-1) arbitrary hydrogen atoms from the specific examples of the 2-valent aromatic ring group.

The (n +1) -valent aromatic ring group may further contain a substituent.

Examples of the substituent which the alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group and (n +1) -valent aromatic ring group may contain include R in the general formula (I)₄₁、R₄₂And R₄₃The alkyl groups mentioned in (1); alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; aryl groups such as phenyl.

As a result of X₄Represented by-CONR₆₄-(R₆₄Represents a hydrogen atom or an alkyl group)₆₄Examples of the alkyl group (b) include alkyl groups having not more than 20 carbon atoms such as a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group, which may have a substituent, and more preferably alkyl groups having not more than 8 carbon atoms.

As X₄Preferably a single bond, -COO-or-CONH-, more preferably a single bond or-COO-.

As L₄The alkylene group in (1) is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group, which may have a substituent.

As Ar₄The aromatic ring group having 6 to 18 carbon atoms, which may have a substituent, is preferable, and a benzene ring group, a naphthalene ring group, or a biphenylene (biphenylene) ring group is more preferable.

The repeating unit represented by the general formula (I) preferably has a hydroxystyrene structure. Namely, Ar₄Preferably a benzene ring group.

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

Repeating units containing an organic group having a polar group

The resin P may further contain a repeating unit containing an organic group having a polar group, particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. Therefore, the substrate adhesion and the developer affinity are improved.

As the alicyclic hydrocarbon structure substituted with a polar group, an adamantyl group, a diamondyl group, or a norbornyl group is preferable. As the polar group, a hydroxyl group or a cyano group is preferable.

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

A repeating unit represented by the general formula (VI)

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

[ chemical formula 4]

In the general formula (VI), the compound represented by the formula (VI),

R₆₁、R₆₂and R₆₃Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Wherein R is₆₂May be reacted with Ar₆Bonded to form a ring, in which case R₆₂Represents a single bond or an alkylene group.

X₆Represents a single bond, -COO-or-CONR₆₄-。R₆₄Represents a hydrogen atom or an alkyl group.

L₆Represents a single bond or an alkylene group.

Ar₆An aromatic ring group having a (n +1) valence, when substituted with R₆₂And (n +2) -valent aromatic ring groups when bonded to form a ring.

When N is greater than or equal to 2, Y₂Are respectively independentAnd (b) represents a group which is removed by the action of a hydrogen atom or an acid. Wherein, Y₂At least 1 of which represents a group that is removed by the action of an acid.

n represents an integer of 1 to 4.

As a group Y leaving by the action of an acid₂The structure represented by the following general formula (VI-A) is preferable.

[ chemical formula 5]

L₁And L₂Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining an alkylene group and an aryl group.

M represents a single bond or a 2-valent linking group.

Q represents an alkyl group, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group.

Q、M、L₁At least 2 of which may 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 a repeating unit represented by the following general formula (3).

[ chemical formula 6]

In the general formula (3), in the formula,

Ar₃represents an aromatic ring group.

R₃Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group or a heterocyclic group.

M₃Represents a single bond or a 2-valent linking group.

Q₃Represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.

Q₃、M₃And R₃At least 2 of which may be bonded to form a ring.

Ar₃The aromatic ring group represented by (VI) and Ar in the general formula (VI) wherein n in the general formula (VI) is 1₆Likewise, phenylene or naphthylene is preferred, and phenylene is more preferred.

Repeating units containing silicon atoms in side chains

The resin P may further contain a repeating unit having a silicon atom on a side chain. Examples of the repeating unit containing a silicon atom include a repeating unit of a (meth) acrylate containing a silicon atom, a repeating unit of a vinyl containing a silicon atom, and the like. The repeating unit having a silicon atom in a side chain is typically a repeating unit having a group having a silicon atom in a side chain, and examples of the group having a silicon atom include trimethylsilyl group, triethylsilyl group, triphenylsilyl group, tricyclohexylsilyl group, tris (trimethylsiloxysilyl group), tris (trimethylsilylsilyl group), methyldimethylsilyl group, dimethyltrimethylsilylsilyl group, and cyclic or linear polysiloxanes or cage-type or ladder-type or random silsesquioxane structures as described below. In the formula, R and R¹Each independently represents a substituent having a valence of 1. Denotes a bond.

[ chemical formula 7]

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

When the resin P contains the repeating unit having a silicon atom in a side chain, the content thereof is preferably 1 to 30 mol%, more preferably 5 to 25 mol%, and further preferably 5 to 20 mol% with respect to all repeating units in the resin P.

The weight average molecular weight of the resin P is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and further preferably 5,000 to 15,000 in terms of polystyrene by GPC (Gel permeation chromatography). When the weight average molecular weight is 1,000 to 200,000, deterioration of heat resistance and dry etching resistance is prevented, and deterioration of developability or deterioration of film forming property due to increase in viscosity is prevented.

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

As other components contained in the chemical solution (for example, an acid generator, a basic compound, a quencher (quencher), a hydrophobic resin, a surfactant, a solvent, and the like), known components can be used.

(high boiling point organic component)

The chemical solution also preferably contains a high-boiling organic component having a boiling point of 250 ℃ or higher. The high-boiling organic component is an organic compound contained in an amount of 10000 ppm by mass or less based on the total mass of the chemical solution. That is, in the present specification, the organic compound having a boiling point of 250 ℃ or higher contained in a content of 10000 ppm by mass or less relative to the total mass of the chemical solution corresponds to the high-boiling organic component, and does not correspond to the organic solvent or the like.

The boiling point of the high-boiling organic component is a boiling point at normal pressure.

When the chemical liquid contains a high-boiling organic component, the content thereof is preferably 0.01 to 500000 mass ppt, more preferably 0.1 to 100000 mass ppt, and still more preferably 0.1 to 20000 mass ppt, based on the mass of the chemical liquid.

In particular, it is considered that if the content of the high-boiling organic component is 0.1 mass ppt or more, the high-boiling organic component is easily associated as containing a trace amount of the metal component and is easily removed, and that the high-boiling organic component is prevented from remaining as a residue on the object to be processed when the chemical solution is used in the semiconductor production process. Further, it is considered that when the content of the high boiling point organic component is 0.1 mass ppt or more, the metal can be inhibited from dissolving out into the chemical liquid when the chemical liquid comes into contact with the metal (member of the present invention or the like).

Further, it is considered that when the content of the high-boiling organic component is 100000 mass ppt or less, the high-boiling organic component excessively present is easily suppressed from remaining as a residue on the object to be processed when the chemical liquid is used in the semiconductor production process.

In addition, the content of the high boiling point organic component in the chemical solution can be measured by a GC/MS (gas chromatography mass spectrometry) method.

(aqueous liquid medicine)

The aqueous chemical solution contains water in an amount of more than 50 mass%, preferably 51 to 100 mass%, and preferably 51 to 95 mass%, based on the total mass of the solvent contained in the aqueous chemical solution.

The water is not particularly limited, but ultrapure water used in semiconductor production is preferably used, and more preferably, ultrapure water is further purified to reduce inorganic anions, metal ions, and the like.

Alkaline developing solution

The aqueous chemical solution is preferably, for example, an alkaline developer.

The pH of the alkaline developer is preferably 10 or more, more preferably 12 or more, and further preferably 13 or more at 25 ℃.

Organic basic compound

The alkaline developer preferably contains an organic alkaline compound, more preferably a quaternary ammonium hydroxide salt or an amine compound, and still more preferably a quaternary ammonium hydroxide salt.

The content of the organic alkaline compound in the alkaline developer is preferably 0.5 to 10% by mass, more preferably 2 to 5% by mass, based on the total mass of the aqueous chemical solution.

Quaternary ammonium hydroxide salt

Examples of the quaternary ammonium hydroxide salt include compounds represented by the following formula (a 1).

[ chemical formula 8]

In the above formula (a1), R^a1～R^a4Independently represents an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, an aralkyl group having 7 to 16 carbon atoms or an aralkyl group having 1 to 16 carbon atomsA hydroxyalkyl group. R^a1～R^a4At least 2 of which may be bonded to each other to form a cyclic structure, in particular, R^a1And R^a2Combination of (1) and R^a3And R^a4At least one of the combinations of (a) may be bonded to each other to form a ring structure.

Among the compounds represented by the above formula (a1), at least 1 selected from the group consisting of tetramethylammonium hydroxide, benzyltrimethylammonium hydroxide, tetrabutylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, methyltripropylammonium hydroxide, methyltributylammonium hydroxide, ethyltrimethylammonium hydroxide, dimethyldiethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, (2-hydroxyethyl) trimethylammonium hydroxide and spiro- (1, 1') -bipyrrolidinium hydroxide is preferable from the viewpoint of easy availability.

Other ingredients

The aqueous chemical solution (including the alkaline developer) may contain other components than the organic alkaline compound. Examples of the other components include a metal component (the same and preferred content as described above in the organic solvent-based chemical liquid), an oxidizing agent, an inorganic acid other than the above-described components as the aqueous chemical liquid, a corrosion inhibitor other than the above-described components as the aqueous chemical liquid, a surfactant, an organic solvent, and a high-boiling-point organic component (the same and preferred content as described above in the organic solvent-based chemical liquid), and the like.

< inert gas >

It is also preferable that the space of the member of the present invention (particularly, the space in the container in the chemical liquid container of the present invention) is filled with an inert gas.

The void portion is, for example, a space in the chemical liquid container not filled with the chemical liquid in the container.

The inert gas is, for example, a gas containing a stable gas with high purity, which is separated and purified from impurities such as water and/or oil.

More specifically, the inert gas is a gas containing a stable gas (a rare gas (helium, neon, argon, krypton, hernia), nitrogen, or the like) at a purity of 95 vol% or more. The purity is preferably 99.9 vol% or more, more preferably 99.999 vol% or more, and further preferably more than 99.9999 vol%. The upper limit is not particularly limited, and is, for example, 99.99999 vol%.

The gap of the chemical liquid container is preferably within the above-mentioned range of purity and the above-mentioned stable gas is present.

The void ratio (volume occupied by the void) in the container of the chemical liquid container is preferably 2 to 80 vol%, more preferably 2 to 50 vol%, and still more preferably 5 to 30 vol%.

The porosity is calculated by the following equation (1).

Formula (1): porosity {1- (volume of chemical solution in container/container volume of container) } × 100

The meaning of the container volume is the same as the inner volume (capacity) of the container.

If the porosity is reduced to a certain extent, the amount of air present in the voids is small, and therefore the amount of the chemical liquid mixed with organic compounds and the like in the air is reduced, and the composition of the stored chemical liquid is easily stabilized.

When the porosity is 2 vol% or more, the liquid chemical can be easily handled because of an appropriate space.

[ manufacturing apparatus ]

The manufacturing apparatus according to the embodiment of the present invention is an apparatus for manufacturing a chemical solution, and includes, for example, at least 1 of a group consisting of a reaction tank, a distillation column, a filter unit, a storage tank, and a pipe, in which at least a part of the liquid-receiving portion is a predetermined member.

Examples of the production apparatus include a reaction apparatus as a production apparatus for reacting raw materials to obtain a chemical solution as a reactant, and a purification apparatus as a production apparatus for purifying a material to be purified to obtain a chemical solution as a purified material.

In addition, the reaction apparatus and the purification apparatus are preferably used in combination, and for example, a chemical solution as a reactant obtained by using the reaction apparatus may be used as a material to be purified, and a chemical solution as a purified material may be obtained by using the purification apparatus.

In addition, when a chemical solution (e.g., a chemical solution as a reactant) is used as a material to be purified, "a chemical solution as a purified material" generally means a chemical solution in which "a chemical solution as a purified material (e.g., a chemical solution as a reactant)" is purified to a higher degree.

According to the manufacturing apparatus using the method for manufacturing a chemical liquid of the present invention, a chemical liquid having excellent residue defect suppression properties and bridging defect suppression properties can be obtained. In addition, even when filtration is performed in the manufacturing process, the life of the filter used can be increased.

Hereinafter, a method for producing (purifying) a chemical solution using a production apparatus (purifying apparatus 30) which is one mode of a chemical solution production apparatus will be described.

The chemical purifying apparatus 30 shown in fig. 2 includes a production tank 31, a filter unit 32, and a filling device 34 (hereinafter, these are also referred to as "units"), and these are connected by a pipe 33. The conduit 33 includes a pump 35, valves 36 and 37, and is formed such that: the purified material or the liquid medicine inside the purifying apparatus 30 can be transferred between the units by operating or opening/closing them.

The filter unit 32 includes a filter housing and a filter accommodated in the filter housing. The filter is not particularly limited, and a depth filter, a screen filter (screen filter), and the like known as a filter for purifying a drug solution can be used. In addition, a pleated filter may be used. Preferred embodiments of the material of the filter will be described later.

The tank 31 stores the liquid medicine. The tank is used, for example, when temporarily storing a chemical liquid (including a chemical liquid (a substance to be purified) before or during purification) in a purification process or a reaction process described later.

The chemical purifying apparatus 30 of fig. 2 includes 1 filter unit 32, but is not limited to this, and may include a plurality of filter units, and the arrangement thereof may be in series with the pipeline, in parallel with the pipeline, or in a combination thereof.

The filling device 34 has a function of filling the container with the chemical liquid. The form is not particularly limited, and a known filling device can be used.

In the chemical liquid manufacturing apparatus 30, the liquid receiving portion of the tank 31 is constituted by a predetermined member, the liquid receiving portion of the filter unit 32 is constituted by a predetermined member, and the liquid receiving portion of the pipe line 33 is constituted by a predetermined member. That is, the liquid-receiving portions of the tank 31, the filter unit 32, and the pipe line 33 are constituted by designated members. In the filter unit 32, the liquid contact portion of the filter case is formed of the above-described predetermined member.

In the above description, the liquid-receiving portions of the tank, the filter unit (particularly, the filter housing), and the pipe are constituted by the predetermined member over the entire surface thereof, but the present invention is not limited to this embodiment. For example, a part of the liquid receiving portion of the tank may be constituted by a predetermined member. Further, a part of the liquid contact portion of the filter unit (particularly, the filter housing) may be formed of a predetermined member. Further, a part of the liquid receiving portion of the pipe may be constituted by a predetermined member.

As described above, at least a part of the liquid-contacting portion of at least 1 structure selected from the group consisting of the tank, the filter unit, and the pipe may be constituted by a predetermined member. Among these, it is preferable that 70% or more of the entire surface area of the liquid-contacting portion of the structure is constituted by the predetermined member, more preferably 80% or more of the entire surface area of the liquid-contacting portion is constituted by the predetermined member, still more preferably 90% or more of the entire surface area of the liquid-contacting portion is constituted by the predetermined member, and particularly preferably the entire surface of the liquid-contacting portion is constituted by the predetermined member.

The liquid-receiving portion of the filter unit will be described with reference to fig. 3 to 5.

Fig. 3 is a perspective view of a typical filter provided in the filter unit, with a part removed. In the filter 40, a cylindrical filter material 41 and a cylindrical core 42 supporting the filter 41 are disposed inside the cylindrical filter material. The cylindrical core 42 is formed in a mesh shape so that liquid can easily pass therethrough. The filter material 41 and the core 42 are concentric. A cover 43 is disposed above the cylindrical filter material 41 and the core 42 so as not to allow liquid to enter from above. A liquid outlet 44 for extracting liquid from the inside of the core 42 is disposed at a lower portion of the filter material 41 and the core 42.

The liquid (purified product) flowing into the filter 40 is blocked by the cover 43, passes through the filter material 41 and the core 42, flows into the core 42, and flows out of the filter 40 through the liquid outlet 44.

In the filter 40, the core 42 is disposed inside the filter material 41, but the filter is not limited to the above-described embodiment, and a Protector (Protector) may be provided outside the filter material 41 (the same form as the core 42, but with a different radius).

Fig. 4 is a perspective view of a housing 50 provided in the filter unit of the present invention, and fig. 5 is a partial sectional view of the housing. The housing 50 is composed of a cover 51 and a body 52, and the cover 51 can be fitted to the body 52. When the cover 51 is fitted to the body 52, the cavity L is formed therein, and therefore the filter 40 can be accommodated in the cavity L.

The casing 50 has a liquid inlet 53 and a liquid outlet 54, and the liquid outlet 44 of the filter 40 and the liquid outlet 54 of the casing are connected by an internal pipe 55 provided inside the cover 51. The flow direction of the purified material is from F₁And (4) showing. The purified material flowing in from the liquid inlet 53 flows into the main body 52 through the internal pipe 56 provided inside the cover 51, passes through the filter material and the core from the outer surface of the filter 40, flows into the core, and is purified in the process.

The purified liquid flowing into the core is carried out of the housing 50 from the liquid outlet of the filter 40 via the internal pipe 55 and the liquid outlet 54 (indicated by F in fig. 2)₂The indicated flow direction).

In fig. 4 and 5, the liquid inlet 53 and the liquid outlet 54 are disposed on the cover 51 of the casing 50, but the casing provided in the filter unit according to the embodiment of the present invention is not limited thereto, and the liquid inlet 53 and the liquid outlet 54 may be disposed at any position of the casing 50. In this case, the liquid inlet 53 may be disposed so that the purified material flows into the filter 40 from the outside of the filter 40, and the liquid outlet 54 may be disposed so that the purified material is extracted from the inside of the core of the filter 40.

In the typical filter unit described above, the "liquid-receiving portion of the filter unit" refers to a portion that is in contact with the object to be purified, except for the portion where the liquid is filtered by 40. Specifically, the inner wall surface of the casing 50, the liquid outlet 44, and the like.

The form of the member is as described above.

A method for producing (purifying) a chemical solution using a chemical solution production apparatus (purifying apparatus 30) will be described below. The method for purifying the chemical solution using the purification apparatus is not particularly limited, but preferably includes a step of filtering the substance to be purified using a filter provided in the filter unit (purification step).

< purification step >

The purified material is first stored in the storage tank 31.

The shape and capacity of the tank are not particularly limited, and may be appropriately changed according to the amount and/or type of the chemical solution to be produced.

The tank may further include an agitation blade or the like for agitating the stored purified product or the like, but in this case, the liquid contact portion such as the agitation blade is preferably formed by a predetermined member.

When the valve 36 is opened, the purified material stored in the storage tank 31 is pumped by the pump 35 along the direction F₁The direction moves in the line 33 and leads to the filter unit 32. The purified material introduced into the filter unit 32 is purified by the filter material 41 provided in the filter 40. Hereinafter, a preferred embodiment of the filter provided in the filter unit will be described.

A filter

The filter material of the filter is not particularly limited, and a known filter material can be used, and the filter may be in the form of a depth filter or a mesh filter, or may be a pleated filter.

The material of the filter is preferably at least 1 selected from the group consisting of nylon, polyethylene (including those having high density and high molecular weight), polypropylene (including those having high density and high molecular weight), Polyfluorocarbon (e.g., polytetrafluoroethylene: PTFE, etc.), cellulose, diatomaceous earth, polystyrene, and glass.

When the purification apparatus includes 2 or more filter units, the filter material of the filter included in each filter unit is preferably formed of a hydrophobic material and a hydrophilic material. In the present specification, the term "hydrophobic material" means that the surface of the filter material is in contact with water at 25 ℃ at 45 ° or more, and the term "hydrophilic material" means that the surface of the filter material is in contact with water at 25 ℃ at less than 45 °.

In the case of using 2 or more filter units, the filter through which the purified product finally passes is preferably provided with a filter including a filter material made of a hydrophilic material (hereinafter, also referred to as "hydrophilic filter"). The hydrophilic filter has a stronger interaction with impurities contained in the object to be purified, particularly with metal components, and more easily adsorbs the impurities. Therefore, it becomes easy to control the contents of metal particles and metal ions in the purified product after purification to be within a desired range.

When 2 or more filter units are used, the differential pressure before and after passing through each filter unit (hereinafter, also referred to as "filtration differential pressure") is not particularly limited, but is preferably 250kPa or less, and preferably 200kPa or less. The lower limit is not particularly limited, but is preferably 50kPa or more. When the filtration differential pressure is 250kPa or less, excessive pressure can be prevented from being applied to the filter, and therefore the amount of dissolved substances can be reduced.

The relationship between the pore diameters of the respective filter materials is not particularly limited, but preferably differs. The pore diameter of the filter material (hereinafter, also referred to as "2 nd filter material") provided in the filter (hereinafter, also referred to as "2 nd filter material") through which the purified product passes after the passage of the purified product is preferably the same as or smaller than the pore diameter of the filter material (hereinafter, also referred to as "1 st filter material") provided in the filter (hereinafter, also referred to as "1 st filter material") through which the purified product passes first. In the present specification, the pore size of the filter material can be referred to the nominal value of the filter manufacturer. Commercially available FILTERs can be selected from various FILTERs provided by Nihon Pall Ltd., Toyo Roshi Kaisha, Ltd., Nihon Entegris K.K, (original Nippon Mykrolis Corporation) or KITZ MICRO FILTER CORPORATION, for example. Further, a "P-nylon filter (pore diameter: 0.02 μm, critical surface tension: 77 mN/m)" made of polyamide; "PE Kleen filter (pore size 0.02 μm)" made of high density polyethylene (manufactured by Nihon Pall ltd.); (Nihon Pall Ltd.) "PE/Kleen filter (pore diameter of 0.01 μm)" made of high density polyethylene; (manufactured by Nihon Pall ltd.).

When the 2 nd filter medium has a pore size smaller than that of the 1 st filter medium, the ratio of the pore size of the 2 nd filter medium to that of the 1 st filter medium (pore size of the 2 nd filter medium/pore size of the 1 st filter medium) is preferably 0.01 to 0.99, more preferably 0.1 to 0.9, and still more preferably 0.2 to 0.9. By setting the pore diameter of the 2 nd filter material to the above range, fine foreign matters mixed in the chemical solution can be removed more reliably.

In the case where the chemical solution contains an organic solvent, from the viewpoint of suppressing an increase in metal particles and metal ions in the chemical solution when the purified chemical solution is stored, it is preferable that the chemical solution and the material of the filter material satisfy a combination of a relational expression (Ra/R0) ≦ 1 and be purified by a filter material satisfying the relational expression, where Ra and R0 are set to an interaction radius (R0) in hansen solubility parameter space derived from the material of the filter material and a sphere radius (Ra) in hansen space derived from the organic solvent contained in the chemical solution. Preferably (Ra/R0). ltoreq.0.98, more preferably (Ra/R0). ltoreq.0.95. The lower limit is preferably 0.5 or more, more preferably 0.6 or more, and still more preferably 0.7. Although the mechanism is not clear, when the content is within this range, the increase in the content of metal particles and metal ions in the chemical solution during long-term storage can be suppressed.

The combination of the filter and the organic solvent is not particularly limited, but examples thereof include a combination of the filter and the organic solvent disclosed in U.S. Pat. No. 2016/0089622.

Since the filtration pressure has an influence on the filtration accuracy, it is preferable that the pressure pulsation during filtration be as small as possible.

The filtration rate is not particularly limited, but is preferably 1.0L/min/m from the viewpoint of obtaining a chemical solution having more excellent effects of the present invention²Above, more preferably 0.75L/min/m²Above, more preferably 0.6L/min/m²The above.

When the filter is provided with a differential pressure resistance value that ensures the filter performance (i.e., the filter is not damaged), and this value is large, the filtration rate can be increased by increasing the filtration pressure. That is, the upper limit of the filtration rate is usually determined by the differential pressure resistance of the filter, but is usually preferably 10.0L/min/m²The following. On the other hand, the amount of particulate foreign matter or impurities dissolved in the chemical liquid can be effectively reduced by reducing the filtration pressure, and the pressure can be adjusted according to the purpose.

From the viewpoint of obtaining a chemical solution having a more excellent effect of the present invention, the filtration pressure is preferably 0.001 to 1.0MPa, more preferably 0.01 to 0.4MPa, and still more preferably 0.05 to 0.2 MPa. In particular, when a filter material having a small pore size is used, the amount of particulate foreign matter or impurities dissolved in the chemical solution can be effectively reduced by reducing the pressure of filtration. In the case of using a filter material having a pore diameter of less than 20nm, the pressure of filtration is particularly preferably 0.05 to 0.2 MPa.

Further, as the pore diameter of the filter material becomes smaller, the filtration rate decreases. However, since a plurality of filters of the same kind are connected in parallel, the filtering area increases and the filtering pressure decreases, so that it is possible to compensate for the decrease in the filtering speed.

The purification step more preferably has the following steps. The purification step may be performed 1 or less times, or may be performed a plurality of times. The order of the following steps is not particularly limited.

1. Particle removal step

2. Metal ion removal step

3. Organic impurity removal step

Hereinafter, the above steps will be described separately.

(particle removal step)

The purification step may include a particle removal step. The particle removing step is a step of removing particles in the chemical liquid containing the organic solvent using a particle removing filter.

The form of the particle removal filter is not particularly limited, but examples thereof include a filter having a filter material with a pore diameter of 20nm or less.

The pore diameter of the filter material is preferably 1 to 15nm, more preferably 1 to 12 nm. When the pore diameter is 15nm or less, further fine particles can be removed, and when the pore diameter is 1nm or more, the filtration efficiency is improved.

Examples of the material of the filter material provided in the particle removal filter include nylon such as 6-nylon and 6, 6-nylon, polyethylene, polypropylene, polystyrene, polyimide, polyamideimide, and polyfluorocarbon.

The polyimide and/or polyamideimide may have at least 1 selected from the group consisting of a carboxyl group, a salt type carboxyl group and an-NH-bond. Regarding the solvent resistance, polyfluorocarbon, polyimide and/or polyamideimide is excellent. In addition, 6-nylon and nylon such as 6, 6-nylon are particularly preferable from the viewpoint of adsorbing metal ions.

In the case where the purification step includes a particle removal step, a plurality of particle removal filters may be used. When a plurality of particle removal filters are used, preferably 1 of the filters is a filter having a filter material with a pore size of 50nm or more (for example, a microfiltration membrane with a pore size of 50nm or more). In the case where fine particles such as colloidal impurities are present in the liquid chemical containing the organic solvent, the liquid chemical containing the organic solvent is filtered using a filter having a filter material with a pore size of 50nm or more (for example, a fine filtration membrane for removing fine particles with a pore size of 50nm or more) before the liquid chemical is filtered using a filter having a filter material with a pore size of 20nm or less (for example, a fine filtration membrane with a pore size of 20nm or less), and therefore the filtration efficiency of the filter having a filter material with a pore size of 20nm or less (for example, a fine filtration membrane with a pore size of 20nm or less) is improved, and the particle removal performance is further improved.

(Metal ion removing step)

The purification step may comprise a metal ion removal step. The metal ion removing step is preferably a step of passing the chemical liquid containing the organic solvent through a metal ion adsorption filter.

The metal ion adsorption filter is not particularly limited, and a known metal ion adsorption filter can be exemplified.

Among these, as the metal ion adsorption filter, a filter capable of ion exchange is preferable. Here, examples of the metal ion to be adsorbed include an ion containing a specific metal and an ion containing other metals. The filter material included in the metal ion adsorption filter preferably contains an acid group on the surface thereof from the viewpoint of improving the adsorption performance of metal ions. Examples of the acid group include a sulfonic acid group and a carboxyl group.

Examples of the material of the filter material provided in the metal ion adsorption filter include cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, polyfluorocarbon, and the like. Nylon is particularly preferable from the viewpoint of efficiency of adsorbing metal ions.

(organic impurity removal step)

The purification step may comprise an organic impurity removal step. As the organic impurity removing step, a step of passing the chemical liquid containing the organic solvent through an organic impurity adsorbing filter is preferable.

The organic impurity adsorbing filter is not particularly limited, and a known organic impurity adsorbing filter may be mentioned.

As the filter material provided in the organic impurity adsorption filter, it is preferable that the surface has an organic skeleton capable of interacting with the organic impurities (in other words, the surface is modified by the organic skeleton capable of interacting with the organic impurities) from the viewpoint of improving the adsorption performance of the organic impurities. Examples of the organic framework capable of interacting with organic impurities include a chemical structure capable of reacting with organic impurities to capture the organic impurities by an organic impurity adsorption filter. More specifically, when the purified product contains an n-long alkyl alcohol (structural isomer when a 1-long alkyl alcohol is used as the organic solvent) as the organic impurity, an alkyl group is given as the organic skeleton. When the purified product contains dibutylhydroxytoluene (BHT) as an organic impurity, a phenyl group may be used as an organic skeleton.

Examples of the material of the filter material provided in the organic impurity adsorbing filter include cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, polyfluorocarbon, and the like, which carry activated carbon.

Further, as the organic impurity adsorbing filter, a filter in which an activated carbon described in japanese patent application laid-open nos. 2002-273123 and 2013-150979 is immobilized on a nonwoven fabric can be used.

As the organic impurity adsorbing filter, in addition to the above-described chemisorption (adsorption using an organic impurity adsorbing filter having an organic skeleton on the surface thereof capable of interacting with organic impurities), a physical adsorption method can be applied.

For example, when BHT is contained as an organic impurity in a purified product, the structure of BHT is larger than 10 angstroms (═ 1 nm). Therefore, by using an organic impurity adsorption filter having a filter material with a pore diameter of 1nm, BHT cannot pass through the pores of the filter material. That is, BHT is physically trapped by the filter and thus removed from the liquid medicine containing the organic solvent. As described above, not only chemical interaction but also physical removal method can be applied to the removal of organic impurities. In this case, a filter having a filter material with a pore size of 3nm or more is used as the "particle removal filter", and a filter having a filter material with a pore size of less than 3nm is used as the "organic impurity adsorption filter".

(cleaning step: step of cleaning Filter)

The method for purifying a chemical solution according to the embodiment of the present invention preferably further includes a step of cleaning the filter. The method for cleaning the filter is not particularly limited, but a method of immersing the filter in a cleaning liquid, passing the cleaning liquid through the filter, and a combination thereof may be mentioned.

By cleaning the filter, the amount of the component extracted from the filter can be easily controlled so as to satisfy the respective requirements of the test solution, and as a result, a chemical solution having more excellent effects of the present invention can be obtained.

The cleaning liquid is not particularly limited, and a known cleaning liquid can be used. The cleaning liquid is not particularly limited, and water, an organic solvent, and the like can be mentioned. The organic solvent may be an organic solvent that can be contained in the chemical solution, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound (preferably having 4 to 10 carbon atoms) that may have a ring, alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate, and the like.

More specifically, examples of the cleaning liquid include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dimethyl sulfoxide, N-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, propylene carbonate, sulfolane, cyclohexane, cyclohexanone, cycloheptanone, cyclopentanone, 2-heptanone, γ -butyrolactone, and a mixture thereof.

The purified material purified by the filter unit is returned to F by opening the valve 37 and operating the pump 35₂And F₃Flows in the direction and is contained in the container as a chemical liquid in the filling device 34.

And, by operation of the valve 37, can be from F₂Flow direction F₄And the purified material is circulated again to the storage tank 31. In this case, the purified material can be purified again by the filter unit, and a chemical solution having more excellent defect suppressing performance can be obtained.

The liquid-receiving portion of the filling device 34 is not particularly limited, but at least a part of the liquid-receiving portion (preferably 70% or more of the entire surface area of the liquid-receiving portion, more preferably 80% or more of the entire surface area of the liquid-receiving portion, further preferably 90% or more of the entire surface area of the liquid-receiving portion, and particularly preferably the entire surface of the liquid-receiving portion) is preferably a member of the present invention.

[ other embodiments of the manufacturing apparatus ]

Another embodiment of the chemical liquid production apparatus will be described with reference to fig. 6. The manufacturing apparatus (purifying apparatus 70) is a purifying apparatus in which a distillation column 71 is connected to a tank 31 of the purifying apparatus 30 of fig. 2 through a pipe 73.

In the purification apparatus 70, the purified product is introduced into the distillation column 71 from the lower part of the distillation column 71 through a line 72. The purified product introduced into the distillation column 71 is distilled, and the distilled purified product is converted to F₀Flows in the direction and is introduced into the storage tank 31. For the purification steps following this, as described above.

In the chemical purifying apparatus 70, the liquid receiving portion of the distillation column 71 is constituted by a predetermined member, the liquid receiving portion of the pipe 73 is constituted by a predetermined member, the liquid receiving portion of the tank 31 is constituted by a predetermined member, the liquid receiving portion of the filter unit 32 is constituted by a predetermined member, and the liquid receiving portion of the pipe 33 is constituted by a predetermined member. That is, the liquid-receiving portions of the distillation column 71, the pipeline 73, the tank 31, the filter unit 32, and the pipeline 33 are constituted by predetermined members. In the filter unit 32, the liquid contact portion of the filter case is formed of the above-described predetermined member.

In the above description, the distillation column, the storage tank, the filter unit (particularly, the filter housing), and the pipeline are configured such that the entire surface of the liquid contact portion is constituted by the predetermined member, but the present invention is not limited to this configuration. For example, a part of the liquid-receiving portion of the distillation column may be constituted by a predetermined member. A part of the liquid receiving portion of the tank may be constituted by a predetermined member. Further, a part of the liquid contact portion of the filter unit (particularly, the filter housing) may be formed of a predetermined member. Further, a part of the liquid receiving portion of the pipe may be constituted by a predetermined member.

As described above, at least a part of the liquid-contacting portion of at least 1 structure selected from the group consisting of a distillation column, a storage tank, a filter unit, and a pipeline may be constituted by a predetermined member. Among these, it is preferable that 70% or more of the entire surface area of the liquid-contacting portion of the structure is constituted by the predetermined member, more preferably 80% or more of the entire surface area of the liquid-contacting portion is constituted by the predetermined member, still more preferably 90% or more of the entire surface area of the liquid-contacting portion is constituted by the predetermined member, and particularly preferably the entire surface of the liquid-contacting portion is constituted by the predetermined member.

As a method for purifying a chemical solution using the apparatus for producing a chemical solution according to the above embodiment, in addition to the method for purifying a chemical solution described above, a distillation process for distilling a purified product using a distillation column may be included, and a purification method using a filter unit only having a distillation process may be omitted.

The following describes the manufacturing apparatus according to the embodiment of the present invention with reference to fig. 7. FIG. 7 is a schematic view of an apparatus for producing a chemical solution. The chemical liquid production apparatus 80 is connected to a reaction tank 81 (which will be collectively referred to as a "reaction section") having a raw material input section 82 through a pipe 72 having a valve 83 to the distillation column 71 of the purification apparatus 70 described in fig. 6. Although the apparatus for producing a chemical in fig. 7 includes the distillation column 71, the apparatus is not limited thereto and may not include the distillation column 71. In this case, for example, the following modes are given: the storage tank 31 of the purification apparatus 30 shown in fig. 2 is connected to a reaction tank 81 having a raw material input unit 82 through a pipe 72 having a valve 83.

The manufacturing apparatus 80 may further include a storage tank for storing the raw material and obtaining a chemical solution as a reactant by performing a reaction before or during the reaction. In addition, the raw material stored in the storage tank for storing the raw material refers not only to the starting raw material but also to an intermediate raw material of the manufacturing process. A part of the liquid-receiving portion of the tank (preferably 70% or more of the entire surface area of the liquid-receiving portion, more preferably 80% or more of the entire surface area of the liquid-receiving portion, still more preferably 90% or more of the entire surface area of the liquid-receiving portion, and particularly preferably the entire surface of the liquid-receiving portion) may be constituted by a predetermined member.

The reaction part has the following functions: the raw material supplied from the raw material charging unit 82 is reacted in the reaction tank 81 (in the presence of a catalyst as necessary) to obtain a reactant containing an organic solvent.

The liquid-contacting portions of the reaction tank 81 and the raw material input portion 82 are not particularly limited, but at least a part of the liquid-contacting portions is preferably constituted by a predetermined member.

In the chemical liquid manufacturing apparatus 80, the liquid receiving portion of the reaction tank 81 is constituted by a predetermined member, the liquid receiving portion of the pipe line 72 is constituted by a predetermined member, the liquid receiving portion of the distillation column 71 is constituted by a predetermined member, the liquid receiving portion of the pipe line 73 is constituted by a predetermined member, the liquid receiving portion of the tank 31 is constituted by a predetermined member, the liquid receiving portion of the filter unit 32 is constituted by a predetermined member, and the liquid receiving portion of the pipe line 33 is constituted by a predetermined member. That is, the liquid-receiving portions of the reaction tank 81, the pipe 72, the distillation column 71, the pipe 73, the tank 31, the filter unit 32, and the pipe 33 are constituted by predetermined members. In the filter unit 32, the liquid contact portion of the filter case is formed of the above-described predetermined member.

In the above description, the entire surface of the liquid-receiving portion of each of the reaction tank, the distillation column, the storage tank, the filter unit (particularly, the filter housing), and the pipeline is constituted by the predetermined member, but the present invention is not limited to this form. For example, a part of the liquid-contacting portion of the reaction tank may be constituted by a predetermined member. A part of the liquid-receiving portion of the distillation column may be constituted by a predetermined member. A part of the liquid receiving portion of the tank may be constituted by a predetermined member. Further, a part of the liquid contact portion of the filter unit (particularly, the filter housing) may be formed of a predetermined member. Further, a part of the liquid receiving portion of the pipe may be constituted by a predetermined member.

As described above, at least a part of the liquid-contacting portion of at least 1 structure selected from the group consisting of a reaction tank, a distillation column, a storage tank, a filter unit, and a pipeline may be constituted by a predetermined member. Among these, it is preferable that 70% or more of the entire surface area of the liquid-contacting portion of the structure is constituted by the predetermined member, more preferably 80% or more of the entire surface area of the liquid-contacting portion is constituted by the predetermined member, still more preferably 90% or more of the entire surface area of the liquid-contacting portion is constituted by the predetermined member, and particularly preferably the entire surface of the liquid-contacting portion is constituted by the predetermined member.

< method for producing chemical solution >

Preferably, the chemical liquid is produced using a chemical liquid production apparatus in which at least a part of the liquid-receiving portion is a predetermined member and which includes at least 1 of the group consisting of a reaction tank, a distillation column, a filter unit, a storage tank, and a pipe. The chemical liquid production apparatus is as described above. The chemical liquid to be produced can be exemplified in the same manner as the above-mentioned examples of the chemical liquid to be contained in the chemical liquid container.

The method for producing the chemical solution using the above-mentioned production apparatus is not particularly limited, but preferably includes the following steps.

Reaction step

Purification step

Here, the purification step is the same as the already described method, and therefore, the description is omitted, and the reaction step will be described below.

The reaction step is a step of reacting the raw materials to obtain a reactant.

The reaction product is not particularly limited, but examples thereof include a purified product containing the above-mentioned organic solvent. That is, a step of synthesizing an organic solvent to obtain a purified product containing the organic solvent is exemplified.

The method for obtaining the reactant is not particularly limited, and a known method can be used. For example, a method of reacting 1 or more kinds of raw materials in the presence of a catalyst to obtain a reactant is mentioned.

More specifically, examples thereof include: a step of reacting acetic acid with n-butanol in the presence of sulfuric acid to obtain butyl acetate; in Al (C)₂H₅)₃A step of reacting ethylene, oxygen and water in the presence of (A) to obtain 1-hexanol; a step of reacting cis-4-methyl-2-pentene in the presence of Ipc2BH (Diisopinocampheylborane: Diisopinocamphylborane) to obtain 4-methyl-2-pentanol; a step of reacting propylene oxide, methanol and acetic acid in the presence of sulfuric acid to obtain PGMEA (propylene glycol 1-monomethyl ether 2-acetate); a step of reacting acetone and hydrogen in the presence of copper oxide-zinc oxide-alumina to obtain IPA (isopropyl alcohol); and a step of obtaining ethyl lactate by reacting lactic acid with ethanol。

Examples

The present invention will be described in further detail below with reference to examples. The materials, the amounts used, the ratios, the treatment contents, the treatment processes, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the examples shown below.

In addition, when the chemical solutions of examples and comparative examples were prepared, the treatment of the container, the preparation of the chemical solution, the filling, the storage, and the analysis and measurement were performed in a clean room satisfying ISO class 2 or 1. In order to improve the measurement accuracy, when the measurement of the content of the organic compound and the measurement of the content of the metal component are performed by ordinary measurement, the measurement is performed by concentrating the chemical solution and calculating the content by converting the concentration into the concentration of the solution before concentration.

Unless otherwise stated, the equipment used for the test and the like have been subjected to a sufficient cleaning treatment in advance.

EXAMPLE X

[ Container ]

[ preparation of the vessel ]

Under the conditions shown in the subsequent table 1, the container containing SUS304, SUS316, or SUS316L was subjected to surface treatment. Specifically, after the pretreatment in table 1, the electrolytic polishing is performed as needed, and further, the post-treatment 1 and/or the post-treatment 2 are performed.

The electrolyte used for the electrolytic polishing was a mixed solution of 85 mass% phosphoric acid and 98 mass% sulfuric acid in a volume ratio of 4: 3.

When annealing or/and acid treatment is/are performed as the post-treatment, the conditions are as follows.

Annealing of

(800 ℃, 1 hour, 10 ppm by mass water in Ar atmosphere)

In example 08, annealing was performed for 2 times (2 hours).

Acid treatment

(35 mass% hydrochloric acid: 69 mass% nitric acid: 50 mass% hydrofluoric acid: 98 mass% sulfuric acid: 5: 1: 13 (volume ratio), treatment temperature 60 ℃ C.)

[ Table 1]

[ measurement of the Container ]

< Cr/Fe ratio >

The Cr/Fe ratio in the inner wall of the vessel (part) was measured by the method described in the specification. In addition, ESCA used was ESCA-3400 manufactured by Shimadzu Corporation.

The Cr/Fe ratio change caused by the depth change disappeared in all the containers until the depth reached 10nm, and the Cr/Fe ratio at the depth of 10nm was set as the Cr/Fe ratio of the base material of the container.

< surface average roughness >

The surface average roughness (Ra) of the surface of the liquid-receiving portion of the container thus produced was measured by a NanoScope4A manufactured by Veeco, an Atomic Force Microscope (AFM).

[ test ]

Each of the containers subjected to the surface treatment was filled with a chemical solution as described below, and was used as a chemical solution container.

The chemical solution was contained in the container in an amount such that the void ratio became 20 vol%, and the void portion was filled with 99.9999 vol% nitrogen gas.

In each of the chemical solutions B to H, a chemical solution purified so that the content of the high-boiling organic component is 10000 ppt by mass relative to the mass of the chemical solution was used. Then, a chemical solution purified so that the content of the high-boiling organic component is 0.01 mass ppt relative to the mass of the chemical solution was prepared in the chemical solution a, and a predetermined amount of the unpurified chemical solution a was added thereto, and the content of the high-boiling organic component in the chemical solution was adjusted so that the content becomes a desired amount.

After concentrating the chemical solution, the content of the high-boiling organic component in the chemical solution was measured by GC/MS (gas chromatography mass spectrometry).

A: PGMEA: propylene glycol monomethyl ether acetate

B: PGMEA/PGME 7: 3 (propylene glycol monomethyl ether acetate/propylene glycol monomethyl ether 7/3 (mass ratio))

C: nBA (butyl acetate)

D: cyclohexanone

E: IPA (isopropyl alcohol)

F: MIBC (4-methyl-2-pentanol)

G: lactic acid ethyl ester

H: PGMEA/PC 9: 1 (propylene glycol monomethyl ether acetate/propylene carbonate 9/1 (mass ratio) mixed solution)

Alkali liquor: 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution

< Change in content of Metal component >

After the container was filled with the drug solution, it was stored at 40 ℃ for 12 months.

Before and after storage, the content of Fe, Cr or Ni (specific metal particles) in the form of particles having a particle diameter of more than 25nm in the chemical solution was measured, and the change in the content of the specific metal particles due to storage was detected and evaluated according to the following criteria.

The content of the specific metal component in all the chemical solutions before storage treatment is 10 mass ppt or less.

A: the increase is 5 mass ppt or less

B: the increase is more than 5 mass ppt and 10 mass ppt or less

C: the increase is more than 10 mass ppt and not more than 100 mass ppt

D: the increase is more than 100 mass ppt and 300 mass ppt or less

E: increase of more than 300 mass ppt

In addition, the content of the specific metal particles in the liquid medicine was measured by a method using SP-ICP-MS.

The following devices were used.

Manufacturer: PerkinElmer co., Ltd.

The model number: nexion350S

The following analysis software was used for the analysis.

Syngistix nano application module special for SP-ICP-MS

Syngistix for ICP-MS software

< evaluation of chemical solution for suppressing defects >

The following evaluations were performed using a drug solution which was filled into a container and then stored at 40 ℃ for 12 months.

(suppression of residual Defect)

The evaluation of the residual defect is carried out by detecting the number of defects corresponding to a diameter of 0.5 to 17nm as the residual defect using the principle described in Japanese patent application laid-open No. 2009-188333 and the method described in paragraphs 0015 to 0067. That is, SiO was formed on a silicon wafer (Bare-Si) substrate having a diameter of 300mm by a CVD (chemical vapor deposition) method_XNext, a chemical solution layer is formed so as to cover the layer. Then, the SiO solution having the above-mentioned SiO_XA method in which a composite layer of the layer and the chemical liquid layer applied thereon is dry-etched, the obtained projections are irradiated with light, scattered light is detected, the volume of the projections is calculated from the scattered light, and the particle diameter of the particles is calculated from the volume of the projections.

The number of A defects is 100/wafer or less.

The number of B defects exceeds 100/wafer and is less than 200/wafer.

The number of C defects exceeds 200/wafer and is less than 2000/wafer.

D, the number of defects exceeds 2000 per wafer and is less than 10000 per wafer.

The number of E defects exceeds 10000 per wafer.

(stain Defect inhibitory Property)

The chemical solution of example 1 was spin-coated on a silicon wafer (Bare-Si) having a diameter of about 300mm to obtain a wafer on which the chemical solution coating was completed. The apparatus used was Lithius ProZ, and the coating conditions were as follows.

Amount of chemical used in coating: each 2ml

Rotation speed of silicon wafer at coating: 2,200rpm, 60sec

Then, using a wafer inspection apparatus "SP-5" manufactured by KLA-Tencor Corporation and a fully automatic defect inspection sorting apparatus "semvison G6" of Applied Materials Corporation, shape observation was performed on the defects increased after coating among the defects having a size of 19nm or more over the entire surface of the wafer, and foreign substances other than the granular ones were regarded as smear foreign substances.

If the evaluation values are A to C, the evaluation values are of a class that causes no problem in practical use.

The number of A defects is 1/wafer or less.

The number of B defects exceeds 1 per wafer and is less than 10 per wafer.

The number of C defects exceeds 10 per wafer and is 100 per wafer or less.

D, the number of defects exceeds 100 per wafer.

(bridging defect suppressing property)

A chemical solution was used for pattern formation using the resist composition, and the bridging defect suppression performance of the chemical solution was evaluated.

First, a resist composition to be used will be described.

Resist composition

The following components were mixed to obtain a resist composition.

Acid-decomposable resins (resins represented by the following formula (weight average molecular weight (Mw): 7500): the numerical values described in the respective repeating units represent mol%): 100 parts by mass

[ chemical formula 9]

A photoacid generator shown below: 8 parts by mass

[ chemical formula 10]

Quenchers as shown below: 5 parts by mass (the mass ratio is 0.1: 0.3: 0.2 in order from the left). Among the quenchers described below, the polymer type was 0.2 by mass, and the weight average molecular weight (polystyrene equivalent value by Mw and GPC) was 5000. The numerical values described in the respective repeating units represent molar ratios.

[ chemical formula 11]

A hydrophobic resin shown below: 4 parts by mass (mass ratio: 0.5) of the hydrophobic resin represented by formula (1) and the hydrophobic resin represented by formula (2) have a weight average molecular weight (the same as that of polystyrene converted by Mw and GPC) of 7000 and a weight average molecular weight (Mw) of 8000. In each hydrophobic resin, the numerical value described in each repeating unit represents a molar ratio.

[ chemical formula 12]

Solvent:

PGMEA (propylene glycol monomethyl ether acetate): 3 parts by mass

Cyclohexanone: 600 parts by mass

γ -BL (γ -butyrolactone): 100 parts by mass

Test methods

The test method is explained next. First, a silicon wafer of about 300mm is pre-wetted with a chemical solution, and then the resist composition is spin-coated on the pre-wetted silicon wafer. Thereafter, the resist film was dried by heating at 150 ℃ for 90 seconds on a hot plate to form a resist film having a thickness of 9 μm.

The resist film was pattern-exposed through a mask having a line and space pattern in which the line width of the pattern formed after reduction projection exposure and development was 30nm and the space width was 30nm, using an ArF excimer laser scanner (PAS 5500/850C wavelength 248nm, manufactured by ASML) under exposure conditions of NA of 0.60 and σ of 0.75. After the irradiation, the substrate was baked at 120 ℃ for 60 seconds, developed and rinsed, and baked at 110 ℃ for 60 seconds to form a pattern having a line width of 30nm and a space width of 30 nm.

The patterns were obtained by using a length measuring scanning electron microscope (length measuring SEM, CG4600, Hitach-HighTech) with an injection molding amount of 100, and the number of crosslinked defects (bridging defects) between the patterns was measured to determine the number of defects per unit area.

The smaller the number of crosslinked defects between patterns, the more excellent the chemical solution has in inhibiting bridging defects. In addition, the bridging defect inhibitory properties of other chemical solutions were evaluated by the same methods as described above.

The liquid of example 20 was generally used in the prewetting, the liquid of example 19-2 was generally used in the developing, and the liquid of example 19 was generally used in the rinsing, and the chemical liquid to be evaluated was applied to the process described in the column of "step" in the example table and evaluated.

For example, in example 01, the chemical solution of example 01 was used as a pre-wetting solution, the chemical solution of example 19-2 was used as a developing solution, and the chemical solution of example 19 was used as a rinse solution to form a pattern, and the number of bridge defects in the obtained pattern was measured.

In the case where an alkali solution (the chemical solution of example 25 or the chemical solution of comparative example 11) was used as the developing solution, ultrapure water was used as the rinse solution.

A: the number of bridging defects is less than 2/cm²。

B: the number of bridging defects was 2/cm²Above and less than 5 pieces/cm²。

C: the number of bridging defects was 5/cm²More than and less than 10 pieces/cm²。

D: the number of bridging defects was 10/cm²More than and less than 15/cm²。

E: the number of bridging defects was 15/cm²The above.

Table 2 shows the surface structure of each container and the chemical solution contained therein.

Table 3 shows the results of the tests performed using the stored chemical solutions.

In table 3, the column of "high boiling point organic component content" shows the content of high boiling point organic component (mass ppt) with respect to the mass of the chemical solution.

[ Table 2]

[ Table 3]

From the results shown in table 3, it was confirmed that the effects of the present invention are more excellent by the chemical liquid container of the present invention.

Further, it was confirmed that when the surface average roughness of the container was 0.1nm or more, the defect suppressing property of the chemical solution tended to be more excellent (comparison between examples 28 and 29, etc.).

It was found that when the Cr/Fe ratio on the surface of the container is 1.1 to 2.5, the effect of the present invention tends to be more excellent (results of examples 08 to 10, 18 to 24, 26 to 28, etc.).

It was confirmed that the effect of the present invention tends to be more excellent as long as the surface of the container is electropolished (comparison of examples 09 and 15, etc.).

It was confirmed that the effect of the present invention tends to be more excellent if a member subjected to pretreatment in addition to electropolishing is used (comparison between examples 16 and 17, etc.).

It was confirmed that the effect of the present invention is more excellent when the content of the high-boiling organic component in the chemical solution is 0.1 to 100000 mass ppt (preferably 0.1 to 20000 mass ppt) (comparison of examples 02 to 06, etc.).

EXAMPLE Y

[ manufacturing apparatus ]

A chemical liquid was produced using an apparatus for producing a chemical liquid including a reaction vessel, a distillation column, a filter unit, a storage tank, and a pipe line, which included a member subjected to surface treatment in the same manner as the vessel of example 02 or comparative example 03 in example X. That is, the surface properties (Cr/Fe ratio, etc.) of the reaction vessel, distillation column, filter unit, storage tank and piping were the same as those of the vessel of example 02 or comparative example 03. The produced chemical liquid was stored in a container using a member subjected to surface treatment in the same manner as the container of example 02 or comparative example 03 in example X.

In addition, no circulation filtration is performed during production. The above-described manufacturing apparatus also included a filling apparatus, and as the filling apparatus, a filling apparatus including a member subjected to surface treatment, similar to the container of example 02 in example X, was used in all the tests.

The production apparatus includes a reaction tank, a distillation column, a filter unit, a storage tank, and a filling device in this order from the temporary side, and the respective components are connected in series in a pipeline.

Wherein, when the prepared liquid medicine is a mixture of two organic solvents, each organic solvent is prepared respectively until the storage tank is filled. The organic solvent separately produced and stored in the storage tank is filled in a tank (also referred to as a "mixing tank") provided between the storage tank and the filling device at a desired mass ratio to prepare a mixed liquid, and then the mixed liquid (the chemical liquid) is filled in a container via the filling device in the same manner as other chemical liquids.

That is, the manufacturing apparatus for manufacturing a mixture of two kinds of organic solvents as a chemical liquid includes two sets of structures in which "a reaction tank, a distillation column, a filter unit, and a storage tank" are connected in series in parallel, and the two are combined in a mixing tank. The mixing tank is further connected to a filling device so that the mixed liquid (chemical liquid) can be filled in the container.

The mixing tank is an embodiment of a storage tank, and includes a surface-treated member in the same manner as the container of example 02.

In the filter unit, an ion exchange filter manufactured by NIHON PALL Corporation was provided to a filter housing, which was surface-treated in the same manner as the container of example 02 or comparative example 03, and used.

Table 4 shows the structure of the manufacturing apparatus.

The chemical solutions produced were as follows.

A: PGMEA: propylene glycol monomethyl ether acetate

B: PGMEA/PGME 7: 3 (propylene glycol monomethyl ether acetate/propylene glycol monomethyl ether 7/3 (mass ratio))

C: nBA (butyl acetate)

D: cyclohexanone

E: IPA (isopropyl alcohol)

F: MIBC (4-methyl-2-pentanol)

G: lactic acid ethyl ester

H: PGMEA/PC 9: 1 (propylene glycol monomethyl ether acetate/propylene carbonate 9/1 (mass ratio) mixed solution)

Alkali liquor: 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution

The chemical solutions were prepared as follows.

A(PGMEA)：

Propylene oxide, methanol and acetic acid are reacted in the presence of sulfuric acid.

B(PGMEA/PGME＝7∶3)：

Propylene oxide, methanol and acetic acid were reacted in the presence of sulfuric acid to produce PGMEA. Then, propylene oxide and methanol were reacted in the presence of sulfuric acid to produce PGME.

C(nBA)：

Acetic acid is reacted with n-butanol in the presence of sulfuric acid.

D (cyclohexanone):

cyclohexane is subjected to an oxidation reaction in the presence of cobalt.

E(IPA)：

Acetone and hydrogen are reacted in the presence of copper oxide-zinc oxide-alumina.

F(MIBC)：

Cis-4-methyl-2-pentene was reacted in the presence of Ipc2BH (Dipinococcophylerane).

G (ethyl lactate):

lactic acid and ethanol were reacted.

H(PGMEA/PC＝9∶1)：

Propylene oxide, methanol and acetic acid were reacted in the presence of sulfuric acid to produce PGMEA. Then, the acidified propylene ester is reacted with carbon dioxide to produce PC.

In addition, the reaction vessel and the distillation column were not used in the production of the alkali solution. TMAH (tetramethylammonium hydroxide) is dissolved to prepare pure water as an alkaline solution, and the solution is passed through a filter unit, a storage tank, and a filling device in this order and filled in a container.

[ test ]

The following evaluations were performed using the drug solutions filled in the containers and stored at 23 ℃ for 3 days.

< content of high-boiling organic component >

The contents of high-boiling organic components in the produced chemical solutions were measured by GC/MS (gas chromatography mass spectrometry).

< content of Metal component >

The content of the specific metal component in the produced chemical liquid was measured by ICP-MS and evaluated according to the following criteria.

A: the content of the specific metal component in the medicinal liquid is 10 mass ppt or less

B: the content of the specific metal component in the chemical solution is more than 10 mass ppt and not more than 30 mass ppt

C: the content of the specific metal component in the chemical solution is more than 30 mass ppt and less than 100 mass ppt

D: the content of the specific metal component in the chemical solution is more than 100 mass ppt and less than 500 mass ppt

E: the content of the specific metal component in the medicinal liquid exceeds 500 mass ppt

< evaluation of chemical solution for suppressing defects >

The manufactured chemical liquid was evaluated for defect suppression by the same method and standard as those in example X.

< evaluation of Filter Life (ion exchange Filter Life) >

The chemical solutions were continuously produced using the production apparatuses shown in table 4. Immediately after the production of the chemical solution was started and the state of the production apparatus was stabilized, the obtained chemical solution was collected as a test sample (initial sample), and thereafter, the chemical solution obtained after the production of a liquid amount of 10000kg was collected as a test sample (aged sample). The collected chemical solution for the test was evaluated by the above-described evaluation method of the residue defect suppression of the chemical solution, the number of defects per unit area was compared with the initial sample, and the flow rate at which the number of defects of the sample became 2 times over time was defined as the "life" of the filter (ion exchange filter). The lifetime of the filter of the manufacturing apparatus of each example for manufacturing the same chemical liquid was evaluated at a ratio, with the lifetime of the manufacturing apparatus of the comparative example used being 1. The results were evaluated by the following criteria.

A: the life is more than 10 times.

B: the life is more than 5 times and 10 times or less.

C: the life is more than 2 times and 5 times or less.

D: the life is more than 1 time and 2 times or less.

E: the life is 1 time or less.

-: comparative example as a comparative object

Table 4 shows the structure of each manufacturing apparatus, and table 5 shows the test results.

Table 4 shows whether or not each component or container of the manufacturing apparatus in the description of "example 2" or "comparative example 3" includes a member subjected to the surface treatment in the same manner as the container of example 02 in example X or a member subjected to the surface treatment in the same manner as the container of comparative example 03.

[ Table 4]

[ Table 5]

From the results shown in table 5, it was confirmed that a chemical liquid having more excellent residue defect inhibitory properties and bridging defect inhibitory properties could be obtained by the method for producing a chemical liquid of the present invention. Further, it was confirmed that the life of the filter used can be maintained for a long period of time even when the filtration is performed in the manufacturing process.

EXAMPLE Z

Containers containing SUS316L or PFA (copolymer of tetrafluoroethylene and perfluoroalkoxyethylene) were surface-treated under the conditions shown in table 6.

Table 7 shows the surface structure of each container after the treatment and the chemical solution contained therein.

In addition, unless otherwise specified, in the subsequent experimental processes, the processes common to those described above are performed in the same order.

Unless otherwise specified, the following descriptions of tables have the same meanings as those of the above-described tables.

[ Table 6]

[ Table 7]

Table 8 shows the chemical solutions contained in the containers and the types of gases filled in the gaps of the containers in the respective test examples. The void ratio of the container in the chemical liquid container was set to 20 vol%.

In the table, the meanings of abbreviations in the respective solvents are as follows.

The content of the high-boiling organic component in each chemical solution (content based on the total mass of the chemical solution) was adjusted to the content (mass ppt) shown in the following table.

A: PGMEA: propylene glycol monomethyl ether acetate

B: PGMEA/PGME 7: 3 (propylene glycol monomethyl ether acetate/propylene glycol monomethyl ether 7/3 (mass ratio))

C: nBA (butyl acetate)

D: cyclohexanone

E: IPA (isopropyl alcohol)

F: MIBC (4-methyl-2-pentanol)

G: lactic acid ethyl ester

I: undecane

J: dimethyl malonate/isoamyl ether 9/1 (mass ratio) mixed liquor

K: dimethyl malonate/isoamyl ether 5/5 (mass ratio) mixed liquor

L: dimethyl malonate/isoamyl ether 1/9 (mass ratio) mixed liquor

M: malonic acid dimethyl ester

In addition, the distance of the Hansen solubility parameter of eicosene relative to PGMEA alone was 9.5MPa^0.5。

Distance of the Hansen solubility parameter relative to eicosene for PGME alone was 11.0MPa^0.5。

Distance of the Hansen solubility parameter of eicosene relative to dimethyl malonate alone was 10.3MPa^0.5。

Distance of the Hansen solubility parameter of eicosene relative to isoamyl ether alone was 2.1MPa^0.5。

In the table, the column "volume resistance value" represents the volume resistivity (Ω m) of the chemical solution. The volume resistivity was measured by the method described in the specification.

The column "HSP distance vs Eikosen" indicates the distance of the Hansen solubility parameter of a drug solution relative to eicosene. In addition, when the drug solution contains 2 kinds of solvents, the value in the column of "HSP distance vs Eikosen" of the drug solution shown in the table is a weighted average of hansen solubility parameters based on the molar ratio of the contents of the respective solvents.

The column "gas type" indicates the type of inert gas filled in the gap of the chemical solution container

The column "vol%" indicates the purity of the inert gas.

[ Table 8]

[ test ]

< evaluation of Charge potential >

After the container was filled with the drug solution, it was stored at 40 ℃ for 12 months. Thereafter, the charge potential of the chemical solution was measured by the same method as described in the specification.

< Change in content of Metal component >

The change in metal content was evaluated in the same manner and with the same criteria as those shown in example X.

< evaluation of chemical solution for suppressing defects >

The following evaluations were performed using a drug solution which was filled into a container and then stored at 40 ℃ for 12 months.

(residue defect suppression, stain defect suppression)

The residue defect suppression and stain defect suppression were evaluated by the same method and criteria as those shown in example X.

(Metal-containing residue defect suppressing ability)

The chemical solution was evaluated for the inhibition of metal-containing residue defects by the following method. In addition, Coat development Track "RF" manufactured by SOKUDO corporation was used in the test^3S”。

The chemical solution was returned to room temperature (23 ℃) after being stored in an atmosphere at 40 ℃ for 12 months after being filled in a container, and the chemical solution was spin-coated on a silicon wafer having a diameter of 300 mm. After drying the silicon wafer, the positions of defects increased by the wafer surface foreign matter inspection apparatus SP-5 manufactured by using the KLA Tencor formula were identified. Regarding each increased defect, whether Fe, Cr and/or Ni were contained was analyzed by Review SEM manufactured by Apried Materials. Among the increased defects, defects containing Fe, Cr and/or Ni were defined as metal-containing residue defects, and the metal-containing residue defect suppression performance of the chemical solution was evaluated by the following criteria.

A: the number of defects in the metal-containing residue is increased to 0 or less per wafer.

B: the number of defects in the metal-containing residue is increased to 1 to 5/wafer.

C: the number of defects in the metal-containing residue defect is increased to 6 or more and 50 or less per wafer.

D: the number of defects of the metal-containing residue defect is increased to 51 or more per wafer.

(bridging defect suppressing property)

The bridging defect suppression performance of the chemical solution was evaluated by the following method.

First, blended resist compositions shown below were prepared.

Resist composition

The resist composition was obtained by mixing the components in the following composition.

Resin (A-1): 0.77g

Photo acid generator (B-1): 0.03g

Basic compound (E-3): 0.03g

PGMEA (commercial product, distillation purification of high purity grade): 67.5g

Ethyl lactate (commercial product, purified by distillation for high purity grade): 75g of

Resin (A)

As the resin, the following resins were used.

[ chemical formula 13]

Photoacid generators

As the photoacid generator, the following compounds were used.

[ chemical formula 14]

Basic compound

As the basic compound, the following compounds were used.

[ chemical formula 15]

Subsequently, AL412 (manufactured by BREWER SCIENCE, INC.) was coated on a silicon wafer having a diameter of 300mm, and baked at 200 ℃ for 60 seconds to form a resist underlayer film having a thickness of 20 nm. A pre-wet solution (obtained by purifying commercially available PGMEA (high purity grade) by distillation) was applied thereon, and a resist composition was applied thereon and baked at 100 ℃ for 60 seconds (PB: Prebake) to form a resist film having a thickness of 30 nm.

The resist film was exposed through a reflective mask using an EUV exposure machine (manufactured by ASML corporation; NXE3350, NA0.33, Dipole 90 °, outer sigma 0.87, inner sigma 0.35). Then, it was heated (PEB: Post Exposure Bake) at 85 ℃ for 60 seconds. Next, a developing solution (obtained by distilling and purifying commercially available butyl acetate (high purity grade)) was sprayed for 30 seconds by a spraying method to develop the silicon wafer, and a rinse solution was discharged for 20 seconds on the silicon wafer by a spin coating method to rinse the silicon wafer. Subsequently, the silicon wafer was rotated at 2000rpm for 40 seconds to form a pattern of lines and spaces having a space width of 20nm and a pattern line width of 15 nm.

As the rinse solution, each of the chemical solutions to be evaluated was used.

Further, when the chemical solution used as the rinse solution is discharged, the chemical solution is transferred from the container to a discharge port of an applicator or the like via a pipe (made by NICIAS Corporation/liquid receiving part: PFA/φ: 4.35mm in inner diameter, 6.35mm in outer diameter/10 m in length/used after previously performing liquid passing cleaning with a cleaning solution obtained by distilling and purifying PGMEA that is commercially available).

An image of the pattern is acquired, and the obtained image is analyzed by the analyzer, and the number of bridging defects per unit area is measured.

(evaluation criteria for bridge Defect suppression)

A: the number of defects is 50 defects/wafer or less.

B: the number of defects is 51/wafer or more and 100/wafer or less.

C: the number of defects is 101 or more and 1000 or less per wafer.

D: the number of defects is 1001/wafer or more.

The results are shown in table 9.

In the table, the term "<. + -. 2 kV" in the column of "charge potential" indicates that the charge potential of the measured chemical solution is within-2 to 2kV and that the term "> +/-2 kV" is out of the range.

[ Table 9]

From the results shown in the table, it was confirmed that even when the member of the present invention is used and brought into contact with a chemical solution having a high volume resistivity, the potential of the charge of the chemical solution in contact therewith is maintained within a range of-2 to 2kV, and the risk of the charge due to the chemical solution can be reduced.

It was confirmed that the metal-containing residue defect suppression property was more excellent when the space of the chemical liquid container was filled with the inert gas (results of example 206, etc.).

The purity of the inert gas is preferably 99.9 vol% or more, and more preferably more than 99.9999 vol% (comparison among examples 201, 202, and 203, etc.).

The distance between the liquid medicine as the organic solvent and the Hansen solubility parameter of the eicosene is 3-20 MPa^0.5The effect of the present invention is more excellent (results of example 213, etc.).

And the distance between the liquid medicine and the eicosene is 3-20 MPa^0.5The organic solvent and the distance of the Hansen solubility parameter relative to the eicosene are not 3 to 20MPa^0.5When the mixing ratio (mass ratio) of the organic solvent (2) is 20/80 to 80/20, the effect of the present invention is more excellent (comparison of examples 214 to 216, etc.).

Description of the symbols

10-lidded container, 11-container, 12, 51-lid, 13-mouth, 14-side, 15-inner wall, 16-outer wall, 30, 70-purification device, 31-storage tank, 32-filter unit, 33, 71, 72, 73-line, 34-filling device, 35-pump, 36, 37, 83-valve, 40-filter, 41-filter material, 42-core, 43-cover, 44-liquid outlet, 50-housing, 52-trunk, 53-liquid inlet, 54-liquid outlet, 55, 56-internal line, 71-distillation column, 80-manufacturing device, 81-reaction tank, 82-raw material input section.