JP7513670B2 - Chemical solution, chemical solution container, kit, and method for manufacturing semiconductor chip - Google Patents

Description

The present invention relates to a chemical solution, a chemical solution container, a kit, and a method for manufacturing semiconductor chips.

During the manufacture of semiconductor devices by a wiring formation process including photolithography, chemical solutions containing water and/or an organic solvent are used as a pre-wet solution, a resist solution (a composition for forming a resist film), a developer, a rinse solution, a stripping solution, a chemical mechanical polishing (CMP) slurry, and a cleaning solution after CMP, or as a dilution solution thereof.
In recent years, progress in photolithography technology has led to progress in miniaturization of patterns. As a method for miniaturizing patterns, a method for shortening the wavelength of an exposure light source is being used, and attempts are being made to form patterns using EUV (extreme ultraviolet) and the like, which have a shorter wavelength, as an exposure light source, instead of ultraviolet light, KrF excimer laser, ArF excimer laser, and the like, which have been conventionally used.
As the patterns to be formed become finer, the above-mentioned chemicals used in this process are required to have a higher defect suppression capability.

As a chemical used in conventional pattern formation, Patent Document 1 discloses "a method for producing an organic processing liquid for patterning a chemically amplified resist film that can reduce particle generation in pattern formation technology (paragraph [0010])."

JP 2015-84122 A

The present inventors have studied the organic processing liquid (chemical liquid) for patterning manufactured by the above manufacturing method, and found that there is room for improvement in terms of defect suppression. More specifically, when the chemical liquid is used as a pre-wet liquid or a rinse liquid, there is room for improvement in suppressing defects such as metal residue defects, particulate organic residue defects, and stain-like residue defects. In addition, when the chemical liquid is used as a pattern developer, there is room for improvement in suppressing defects such as poor development defects, residue defects, and uniformity defects.
An object of the present invention is to provide a chemical solution having excellent defect suppression properties as described above.
Another object of the present invention is to provide a drug solution container, a kit, and a method for manufacturing a semiconductor chip.

As a result of intensive research into solving the above problems, the inventors have discovered that the above problems can be solved by the following configuration.

(1) A chemical solution containing an organic solvent,
Contains at least one first organic compound selected from the group consisting of compounds represented by general formulas (I) to (III) described below,
A chemical solution having a total content of the first organic compounds of 0.01 to 100,000 ppt by mass relative to the total mass of the chemical solution.
(2) The chemical solution according to (1), further comprising at least one second organic compound selected from the group consisting of compounds represented by general formulas (IV) to (VII) described below.
(3) The chemical solution according to (2), which contains at least two or more compounds selected from the first organic compound and the second organic compound.
(4) The drug solution according to (3), wherein at least one of the two or more compounds has a ClogP value of 5 or more.
(5) The drug solution according to any one of (2) to (4), wherein at least one of the two or more compounds contains a compound represented by general formula (VI).
(6) The chemical solution according to (5), wherein the ratio of the content of the compound represented by the general formula (VI) to the total content of the first organic compound and the second organic compound other than the compound represented by the general formula (VI) is 0.01 to 1.
(7) Further containing a metal component,
The chemical solution according to any one of (1) to (6), wherein the content of the metal component is 0.1 to 500 ppt by mass relative to the total mass of the chemical solution.
(8) The chemical solution according to (7), wherein a ratio of the total content of the first organic compound to the content of the metal component is 0.01 to 10,000.
(9) The chemical solution according to (2), further comprising a metal component.
(10) The chemical solution according to (9), wherein a ratio of a total content of the first organic compound and the second organic compound to a content of the metal component is 0.01 to 50,000.
(11) The chemical solution according to (9) or (10), wherein the metal component contains metal particles and metal ions.
(12) The chemical solution according to (11), in which a ratio of a total content of the first organic compound and the second organic compound to a content of the metal particles is 0.01 to 50,000.
(13) The chemical solution according to (11) or (12), wherein a ratio of a total content of the first organic compound and the second organic compound to a content of the metal ion is 0.03 to 30,000.
(14) The organic solvent is propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl methoxypropionate, cyclopentanone, cyclohexanone, γ-butyrolactone, diisoamyl ether, butyl acetate, isoamyl acetate, isopropanol, 4-methyl-2-pentanol, dimethyl sulfoxide, N-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol The drug solution according to any one of (1) to (13), wherein the isocyanate is selected from the group consisting of butyl ether, propylene glycol, ethylene carbonate, propylene carbonate, sulfolane, cycloheptanone, 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, isopentyl 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.
(15) The chemical solution according to any one of (1) to (14), wherein the volume resistivity of the organic solvent is 5,000,000 Ωm or more.
(16) A kit containing two or more selected from the group consisting of a pre-wet liquid containing the chemical liquid according to any one of (1) to (15), a developer containing the chemical liquid according to any one of (1) to (15), a rinse liquid containing the chemical liquid according to any one of (1) to (15), a polishing liquid containing the chemical liquid according to any one of (1) to (15), and a composition for forming a resist film containing the chemical liquid according to any one of (1) to (15).
(17) A method for treating a pulmonary circulation comprising: a container; and a drug solution according to any one of (1) to (15) contained in the container;
A chemical container, the liquid-contacting portion of which comes into contact with the chemical solution in the container being made of electrolytically polished stainless steel or fluororesin.
(18) The drug solution container according to (17), wherein the void ratio in the container calculated by the formula (X) described below is 5 to 30 volume %.
(19) A method for manufacturing a semiconductor chip, comprising the steps of: manufacturing a semiconductor chip by using the chemical solution according to any one of (1) to (15).

According to the present invention, a chemical solution having excellent defect suppression properties can be provided.
The present invention also provides a drug solution container, a kit, and a method for manufacturing a semiconductor chip.

The present invention will be described in detail below.
The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.
In this specification, a numerical range expressed using "to" means a range that includes the numerical values before and after "to" as the lower and upper limits.
In addition, in the present invention, "ppm" means "parts-per-million ( ^10-6 )", "ppb" means "parts-per-billion ( ^10-9 )", "ppt" means "parts-per-trillion ( ^10-12 )", and "ppq" means "parts-per-quadrillion ( ^10-15 )".
In addition, in the description of groups (atomic groups) in the present invention, descriptions that do not indicate whether they are substituted or unsubstituted include groups that do not have a substituent as well as groups that contain a substituent, within the scope of the present invention. For example, a "hydrocarbon group" includes not only a hydrocarbon group that does not have a substituent (unsubstituted hydrocarbon group), but also a hydrocarbon group that contains a substituent (substituted hydrocarbon group). This point is the same for each compound.
In the present invention, "radiation" refers to, for example, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, or electron beams. In the present invention, light refers to actinic light or radiation. Unless otherwise specified, "exposure" in the present invention includes not only exposure to far ultraviolet light, X-rays, EUV, or the like, but also drawing with particle beams such as electron beams or ion beams.

Although the mechanism by which the drug solution of the present invention solves the above problems is not entirely clear, the present inventors speculate on the mechanism as follows: Note that the following mechanism is merely speculation, and even if the effect of the present invention is obtained through a different mechanism, it is still within the scope of the present invention.
A trace amount of impurities may be mixed into the chemical solution during storage and transportation through piping, and such impurities may easily cause various defects. The various defects are, for example, defects that occur when the chemical solution is applied to the manufacturing process of a semiconductor device. More specific examples include metal residue defects, particulate organic residue defects, and stain-like residue defects when the chemical solution is used as a pre-wet solution or a rinse solution, development defects, residue defects, and uniformity defects when the chemical solution is used as a developer for a pattern, and the above-mentioned defects that occur when the chemical solution is used as a pipe cleaning solution and then the pre-wet solution, rinse solution, developer, or the like is transported through a cleaned pipe before use.
Since the chemical solution of the present invention contains a predetermined amount or more of the first organic compound described below, it behaves like a saturated solution, and impurities (especially impurities that are likely to cause defects) are less likely to be mixed into the chemical solution.
On the other hand, by setting the content of the first organic compound to a predetermined amount or less, it is possible to prevent the first organic compound itself from causing defects.
The present inventors speculate that, based on this mechanism, various processes using the chemical solution of the present invention can suppress the occurrence of defects in the final product.

The chemical solution of the present invention contains an organic solvent and at least one first organic compound selected from the group consisting of compounds represented by general formulas (I) to (III) described below, and the total content of the first organic compound is 0.1 to 100,000 ppt by mass with respect to the total mass of the chemical solution.
The components contained in the drug solution of the present invention will be described in detail below.

<Organic Solvent>
The chemical solution of the present invention (hereinafter, also simply referred to as "chemical solution") contains an organic solvent.
In this specification, the organic solvent refers to a liquid organic compound contained in an amount exceeding 10,000 ppm by mass per component relative to the total mass of the chemical solution. In other words, in this specification, a liquid organic compound contained in an amount exceeding 10,000 ppm by mass relative to the total mass of the chemical solution corresponds to an organic solvent.
In addition, in this specification, the term "liquid" means that the material is liquid at 25° C. and atmospheric pressure.

The content of the organic solvent in the chemical solution is not particularly limited, but is preferably 98.00% by mass or more, more preferably more than 99.00% by mass, still more preferably 99.90% by mass or more, and particularly preferably more than 99.95% by mass, based on the total mass of the chemical solution. The upper limit is less than 100% by mass.
The organic solvent may be used alone or in combination of two or more. When two or more organic solvents are used, the total content is preferably within the above range.

The type of organic solvent is not particularly limited, and known organic solvents can be used. Examples of organic solvents include alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactates, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, alkyl pyruvates, dialkyl sulfoxides, cyclic sulfones, dialkyl ethers, monohydric alcohols, glycols, alkyl acetates, and N-alkylpyrrolidones.

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

The volume resistivity of the organic solvent is not particularly limited, but is preferably 500,000,000 Ωm or more. The upper limit is not particularly limited, but is preferably 5,000,000,000 Ωm or less.
The volume resistivity of the organic solvent can be measured, for example, by using a volume resistivity meter SME-8310 or an ultra insulation meter SM-8220 manufactured by Hioki Electric Corporation.

The organic solvent preferably has a Hansen solubility parameter distance to eicosene of, for example, 3 to 20 MPa ^0.5 (more preferably 5 to 20 MPa ^0.5 ).
When two or more organic solvents are used, it is preferable that at least one of them satisfies the above-mentioned range of Hansen solubility parameters.
When two or more organic solvents are used, it is preferable that the weighted average value of the Hansen solubility parameters based on the molar ratio of the contents of the respective organic solvents satisfies the above-mentioned range of the Hansen solubility parameters.

For example, in terms of better defect suppression properties of the chemical solution, it is also preferable that the organic solvent is substantially only an organic solvent that satisfies the above-mentioned Hansen solubility parameter range. "Substantially only an organic solvent that satisfies the above-mentioned Hansen solubility parameter range" means that the content of the organic solvent that satisfies the above-mentioned Hansen solubility parameter range is 99% by mass or more (preferably 99.9% by mass or more) based on the total mass of the organic solvent.

Also, for example, the organic solvent is preferably a mixed solvent containing both an organic solvent that satisfies the above-mentioned range of Hansen solubility parameters and an organic solvent that does not satisfy the above-mentioned range of Hansen solubility parameters.
In this case, from the viewpoint of more excellent defect suppression properties of the obtained chemical solution, it is preferable that the mixed solvent contains 20 to 80% by mass (preferably 30 to 70% by mass) of an organic solvent satisfying the above-mentioned Hansen solubility parameter range, based on the total mass of the mixed solvent, and contains 20 to 80% by mass (preferably 30 to 70% by mass) of an organic solvent not satisfying the above-mentioned Hansen solubility parameter range, based on the total mass of the mixed solvent.
When the content of the organic solvent satisfying the above-mentioned range of Hansen solubility parameters and the content of the organic solvent not satisfying the above-mentioned range of Hansen solubility parameters are each equal to or more than a certain amount, the affinity of the chemical solution for the metal-based material and the organic-based material can be adjusted to an appropriate range, and the effect of the present invention is considered to be better than when the amount of the organic solvent not satisfying the above-mentioned range of Hansen solubility parameters is outside a predetermined range (for example, 1% by mass or more but less than 20% by mass or more or more than 80% by mass with respect to the total mass of the mixed solvent).
In this case, the total content of the organic solvent satisfying the above-mentioned range of Hansen solubility parameters and the organic solvent not satisfying the above-mentioned range of Hansen solubility parameters is preferably 99.0% by mass or more based on the total mass of the mixed solution. Although there is no particular upper limit, it is generally preferably 99.99999% by mass or less.
In addition, in an organic solvent that does not satisfy the above-mentioned range of Hansen solubility parameters, the distance of the Hansen solubility parameter to eicosene is 0 MPa ^0.5 or more and less than 3 MPa ^0.5 (preferably more than 0 MPa ^0.5 and less than 3 MPa ^0.5 ), or more than 20 MPa ^0.5 (preferably more than 20 MPa ^0.5 and 50 MPa ^0.5 or less).

In this specification, the Hansen solubility parameters are intended to mean the Hansen solubility parameters described in "Hansen Solubility Parameters: A Users Handbook, Second Edition" (page 1-310, CRC Press, published in 2007) etc. That is, the Hansen solubility parameters express solubility as a multidimensional vector (dispersion term (δd), dipole-dipole term (δp), and hydrogen bond term (δh)), and these three parameters are considered to be the coordinates of a point in a three-dimensional space called the Hansen space.
The Hansen solubility parameter distance is the distance between two compounds in the Hansen space, and the Hansen solubility parameter distance can be calculated by the following formula:
(Ra) ² = 4(δd2 - δd1) ² + (δp2 - δp1) ² + (δh2 - δh1) ²
Ra: the distance between the Hansen solubility parameters of the first compound and the second compound (unit: MPa ^0.5 )
δd1: Dispersion term of the first compound (unit: MPa ^0.5 )
δd2: Dispersion term of the second compound (unit: MPa ^0.5 )
δp1: dipole term of the first compound (unit: MPa ^0.5 )
δp2: dipole term of the second compound (unit: MPa ^0.5 )
δh1: hydrogen bond term of the first compound (unit: MPa ^0.5 )
δh2: Hydrogen bond term of the second compound (unit: MPa ^0.5 )
In this specification, the Hansen solubility parameter of a compound is specifically calculated using HSPiP (Hansen Solubility Parameter in Practice).

<First organic compound>
The chemical solution contains at least one kind of first organic compound selected from the group consisting of compounds represented by general formulas (I) to (III).

In general formula (I), Y represents a benzene ring group which may be substituted with an alkyl group, or a group represented by general formula (A). In general formula (A), * represents the bonding position.

When Y represents a benzene ring group, s represents 1, L represents a single bond, and R ^1a represents an alkyl group which may contain a substituent. The alkyl group may contain a heteroatom (preferably an oxygen atom). When the alkyl group contains an oxygen atom, it is preferably contained in the form of -O- or -CO-. In other words, the alkyl group may contain -O- or -CO-.
The alkyl group of R ^1a may be linear or branched, or may contain a cyclic structure.
The number of carbon atoms in the alkyl group of R ^1a is preferably 1 to 20, and more preferably 1 to 10. The number of carbon atoms in the alkyl group of R ^1a does not include the number of carbon atoms contained in a substituent that the alkyl group of R ^1a may contain.
The substituent that the alkyl group of R ^1a may contain preferably contains an aromatic ring group (preferably a benzene ring group, which may further contain a substituent), and more preferably the substituent is an aromatic ester group.
When an alkyl group is substituted on the benzene ring group represented by Y, the alkyl group and R ^1a may be bonded to each other to form a ring. When a plurality of alkyl groups are substituted on the benzene ring group represented by Y, the alkyl groups may be bonded to each other to form a ring.

When Y represents a group represented by formula (A), s represents 3, L represents a methylene group, and each R ^1a independently represents an alkyl group.
In this case, the alkyl group of R ^1a preferably has 1 to 15 carbon atoms, and more preferably has 1 to 10 carbon atoms.
Examples of the compound represented by formula (I) are given below.

In formula (II), R ^2a to R ^2h each independently represent an alkyl group which may contain a substituent.
R ^2b and R ^2e may be bonded to each other to form a ring, and the group formed by R ^2b and R ^2e being bonded to each other is preferably —O—(—Si(R ²ⁱ ) ₂ —O—) _a —.
a represents an integer of 1 or more. There is no particular upper limit to a, but a is often 10 or less.
R ²ⁱ represents an alkyl group which may contain a substituent.
A plurality of R ^2i's may be the same or different.
The alkyl groups represented by R ^2a to R ²ⁱ may be linear or branched, or may contain a cyclic structure.
The number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 1 to 5. The number of carbon atoms in the alkyl group does not include the number of carbon atoms in any substituent that the alkyl group may have.
The alkyl groups represented by R ^2a to R ²ⁱ are each independently preferably an unsubstituted alkyl group, and more preferably a methyl group.
It is also preferred that one of R ^2g and R ^2h is an alkyl group containing a substituent. The substituent is preferably a group containing one or more oxyalkylene groups (the alkylene group portion preferably has 2 to 4 carbon atoms, may be linear or branched, or may contain a cyclic structure). The group containing one or more oxyalkylene groups may contain a hydroxyl group.
Examples of the compound represented by the general formula (II) are shown below.

In formula (III), R ^3a represents -N(R ^3c )R ^3d or -SR ^3e .
R ^3c , R ^3d and R ^3e each represent a hydrogen atom or a substituent.
R ^3b represents -NH- or -S-.
Examples of R ^3e include aromatic thio groups. The aromatic thio group is preferably a group represented by -S-Ar (Ar: an aromatic ring group which may have a substituent).
The aromatic ring group in the aromatic thio group may or may not contain a heteroatom (such as a sulfur atom, a nitrogen atom, and/or an oxygen atom), but preferably contains one. In other words, the aromatic ring group is preferably an aromatic heterocyclic group. The aromatic ring group may be a monocyclic or polycyclic ring, but preferably a polycyclic ring.
The aromatic ring group is preferably a benzothiazole ring group.
Examples of the compound represented by the general formula (III) are shown below.

The boiling point of the first organic compound is not particularly limited, but is preferably 250° C. or higher, more preferably 380° C. or higher, in that the first organic compound is less likely to volatilize, forms an association with a metal component, and can further suppress the occurrence of defects derived from the metal component. The upper limit is not particularly limited, but is often 450° C. or lower.
The above boiling point means the boiling point under 1 atmospheric pressure.

The molecular weight of the first organic compound is not particularly limited, but in relation to the boiling point, it is preferably 300 or more. There is no particular upper limit, but it is often 1000 or less.

The ClogP of the first organic compound is not particularly limited, but is preferably 5.0 or more, more preferably 8.0 to 26.0, and even more preferably 8.5 to 20.0.
The ClogP value is a value obtained by calculating the common logarithm logP of the partition coefficient P between 1-octanol and water. Known methods and software can be used to calculate the ClogP value, but unless otherwise specified, the present invention uses the ClogP program incorporated in ChemBioDraw Ultra 12.0 by Cambridge Soft.

The absolute value of the difference between the ClogP of the first organic compound and the ClogP of the organic solvent is not particularly limited, but is preferably 3 or more, and more preferably 5 to 10, in that the first organic compound acts as a hydrophobic compound in the chemical solution and acts with the metal components to further suppress the occurrence of defects due to the metal components.

The total content of the first organic compound is 0.01 to 100,000 ppt by mass relative to the total mass of the chemical solution, and from the viewpoint of better defect suppression of the chemical solution (hereinafter also simply referred to as "better effects of the present invention"), it is preferably 80,000 ppt by mass or less, more preferably 10,000 ppt by mass or less, and even more preferably 2,000 ppt by mass or less. There is no particular lower limit, but it is preferably 0.1 ppt by mass or more, and more preferably 1 ppt by mass or more.
The first organic compound may be used alone or in combination of two or more. In particular, it is preferred to use two or more of them in terms of obtaining better effects of the present invention.

The content of the first organic compound in the chemical solution can be measured using a GCMS (gas chromatography mass spectrometry).

The chemical solution may contain components other than the organic solvent and the first organic compound described above.
The other components are described in detail below.

<Second Organic Compound>
The chemical solution may contain at least one second organic compound selected from the group consisting of the compounds represented by general formulas (IV) to (VIII).

In general formula (IV), X represents a benzene ring group which may contain a substituent, a cyclohexene ring group which may contain a substituent, or a cyclohexane ring group containing a cycloalkyloxy group as a substituent.
The cyclohexane ring group may further contain another substituent, such as a hydrocarbon group (e.g., an unsaturated hydrocarbon group) which may contain at least one type selected from the group consisting of a hydroxyl group and a carboxy group.
Examples of the substituent that the benzene ring group may have include an alkyl group, an alkoxy group, and an arylcarbonyl group, each of which may have a substituent.
Examples of the substituent that the cyclohexene ring group may contain include an alkenyloxy group and a cyclohexene ring group, each of which may contain a substituent.

The compound represented by the general formula (IV) includes a compound represented by the general formula (IV-1).
General formula (IV-1) (HO-Ar-L) ₄ -C
In the above formula, Ar represents a benzene ring group which may contain a substituent. L represents a divalent linking group. Examples of the divalent linking group include an alkylene group which may contain an ester group.

The following is an example of a compound represented by general formula (IV):

In formula (V), R ^5a represents an optionally substituted alkyl group or a hydrogen atom.
R ^5b and R ^5c each independently represent a hydrogen atom, -AL-O-R ^5d , -CO-R ^5e , or -CH(OH)-R ^5f .
AL represents an alkylene group (preferably having 1 to 6 carbon atoms) which may contain a substituent.
R ^5d , R ^5e and R ^5f each independently represent a substituent (preferably an alkyl group which may further contain a substituent).
The alkyl groups which may have a substituent represented by R ^5a , R ^5d , R ^5e , and R ^5f may each independently be linear or branched, or may have a cyclic structure.
The number of carbon atoms in the alkyl group is preferably 1 to 50, and more preferably 1 to 20. The number of carbon atoms in the alkyl group does not include the number of carbon atoms in any substituent that the alkyl group may contain.
Examples of the substituent that the alkyl group may have include a hydroxyl group, an alkyl ester group, and an alkyl vinyl group (preferably an alkyl group portion having 3 to 12 carbon atoms).
When a plurality of R ^5d are present, each of the plurality of R ^5d may be the same or different. When a plurality of R ^5e are present, each of the plurality of R ^5e may be the same or different. When a plurality of R ^5f are present, each of the plurality of R ^5f may be the same or different.
A combination of two selected from the group consisting of a substituent which the alkyl group represented by ^R5a may have, ^R5d , R5e, and ^R5f , two ^R5d 's, two ^R5e 's, or two ^{R5f 's} may be bonded to each other to form a ring.
The substituent which the alkyl group represented by R ^5a may contain, the combination of two selected from the group consisting of R ^5d , R ^5e , and R ^5f , and the group formed by bonding two R ^5d together, two R ^5e together, or two R ^5f together preferably contains one or more linking groups selected from the group consisting of -O-, -NR ^5g - (R ^5g is a substituent), and -NHCO-.
At least one of R ^5a , R ^5b and R ^5c is other than a hydrogen atom.

An example of a compound represented by general formula (V) is a compound represented by general formula (V-1).

In the above formula, L represents an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms) which may contain a substituent. q represents 3 to 10 (preferably 4 to 6).

The following is an example of a compound represented by general formula (V):

In formula (VI), R ^6a and R ^6b each independently represent an alkyl group which may contain a substituent.
The alkyl group may be linear or branched, or may contain a cyclic structure.
The number of carbon atoms in the alkyl group is preferably 1 to 20, and more preferably 2 to 10. The number of carbon atoms in the alkyl group does not include the number of carbon atoms in any substituent that the alkyl group may contain.
The above-mentioned substituent is preferably, for example, an aromatic ring group (which may further contain a substituent, preferably a phenyl group).
Examples of the compound represented by formula (VI) are shown below.

In formula (VII), R ^7a to R ^7c each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a benzene ring group which may have a substituent.
Of R ^7a to R ^7c , one or more (preferably two or more) are preferably an alkyl group which may contain a substituent, or a benzene ring group which may contain a substituent.
The alkyl group may be linear or branched, or may contain a cyclic structure.
The number of carbon atoms in the alkyl group is preferably 1 to 20, and more preferably 1 to 5. The number of carbon atoms in the alkyl group does not include the number of carbon atoms contained in a substituent that the alkyl group may contain. The substituent is preferably an alkoxy group (preferably having a carbon number of 2 to 6) or a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom).
The substituent which the above benzene ring group may have is preferably an alkyl group (preferably having a carbon number of 2 to 10).
Examples of the compound represented by the general formula (VII) are shown below.

The boiling point of the second organic compound is not particularly limited, but is preferably 250° C. or higher, more preferably 380° C. or higher, in that the second organic compound is less likely to volatilize, forms an association with the metal component, and can further suppress the occurrence of defects derived from the metal component. The upper limit is not particularly limited, but is often 450° C. or lower.
The above boiling point means the boiling point under 1 atmospheric pressure.

The molecular weight of the second organic compound is not particularly limited, but in relation to the boiling point, it is preferably 300 or more. There is no particular upper limit, but it is often 2000 or less.

The ClogP of the second organic compound is not particularly limited, but is preferably 5.0 or more, more preferably 8.0 to 26.0, and even more preferably 8.5 to 20.0.

The absolute value of the difference between the ClogP of the second organic compound and the ClogP of the organic solvent is not particularly limited, but is preferably 3 or more, and more preferably 5 to 10, in that the second organic compound acts as a hydrophobic compound in the chemical solution and acts with the metal components to further suppress the occurrence of defects due to the metal components.

The total content of the second organic compound is not particularly limited, but is preferably 0.01 to 100,000 mass ppt relative to the total mass of the chemical solution, in terms of the superior effect of the present invention. Among these, in terms of the superior effect of the present invention, 80,000 mass ppt or less is preferable, 20,000 mass ppt or less is more preferable, 10,000 mass ppt or less is even more preferable, and 2,000 mass ppt or less is particularly preferable. The lower limit is not particularly limited, but is preferably 0.1 mass ppt or more, and more preferably 1 mass ppt or more.
The second organic compound may be used alone or in combination of two or more. In particular, it is preferred to use two or more of them in terms of obtaining better effects of the present invention.

When the chemical solution of the present invention contains the first organic compound and the second organic compound, it is preferable that the chemical solution of the present invention contains at least two or more compounds among the first organic compound and the second organic compound, in terms of better effects of the present invention. For example, the chemical solution of the present invention may contain at least one or more compounds among the first organic compound and at least one or more compounds among the second organic compound.
Of the two or more compounds, it is preferred that at least one compound has a ClogP of 5 or more.

Of the two or more compounds, at least one is preferably a compound represented by the general formula (VI) above.
In this case, the ratio of the total content of the first organic compound and the second organic compound other than the compound represented by general formula (VI) to the content of the compound represented by general formula (VII) is not particularly limited, but is preferably 0.01 to 1.

<Metal Components>
The chemical solution may contain a metal component.
In the present invention, the metal component includes metal particles and metal ions, and for example, the content of the metal component refers to the total content of the metal particles and metal ions.
The chemical solution may contain either metal particles or metal ions, or may contain both, and it is preferable that the chemical solution contains both metal particles and metal ions.

Examples of the metal element in the metal component include Na (sodium), K (potassium), Ca (calcium), Fe (iron), Cu (copper), Mg (magnesium), Mn (manganese), Li (lithium), Al (aluminum), Cr (chromium), Ni (nickel), Ti (titanium), and Zn (zirconium). The metal component may contain one type of metal element or two or more types of metal elements.
The metal particles may be a simple substance or an alloy, and the metal may be present in a form associated with an organic substance.
The metal component may be a metal component that is inevitably contained in each component (raw material) contained in the chemical solution, a metal component that is inevitably contained during the production, storage, and/or transportation of the treatment solution, or a metal component that is intentionally added.

In order to obtain a more excellent defect suppression property of the chemical solution, when the chemical solution contains a metal component, the content thereof is preferably 0.01 to 500 ppt by mass, more preferably 0.01 to 250 ppt by mass, and even more preferably 0.01 to 100 ppt by mass, relative to the total mass of the chemical solution.
When the content of the metal component is 0.01 ppt by mass or more, the metal component is likely to form an association with the first organic compound (or the second organic compound) described above, and is therefore likely to be removed from the substrate, thereby further improving the defect suppression property.
Furthermore, if the content of the metal components is 500 ppt by mass or less, it is easy to avoid an increase in the occurrence of defects resulting from the metal components.

In order to obtain a more excellent defect suppression property of the chemical solution, when the chemical solution contains metal ions, the content thereof is preferably 0.01 to 400 ppt by mass, more preferably 0.01 to 200 ppt by mass, and even more preferably 0.01 to 80 ppt by mass, relative to the total mass of the chemical solution.
In order to obtain a more excellent defect suppression property of the chemical solution, when the chemical solution contains metal particles, the content thereof is preferably 0.01 to 400 ppt by mass, more preferably 0.01 to 150 ppt by mass, and even more preferably 0.01 to 40 ppt by mass, relative to the total mass of the chemical solution.

The types and contents of the specific metal ions and specific metal particles in the chemical solution can be measured by SP-ICP-MS (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry).
Here, the SP-ICP-MS method uses the same equipment as the normal ICP-MS method (inductively coupled plasma mass spectrometry), and differs only in the data analysis. Data analysis of the SP-ICP-MS method can be performed using commercially available software.
In the ICP-MS method, the content of the metal component to be measured is measured regardless of the form in which it exists. Therefore, the total mass of the metal particles and metal ions to be measured is quantified as the content of the metal component.

On the other hand, the SP-ICP-MS method can measure the content of metal particles, and therefore the content of metal ions in a sample can be calculated by subtracting the content of metal particles from the content of metal components in the sample.
An example of an apparatus for the SP-ICP-MS method is Agilent Technologies' Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200), which can be measured by the method described in the Examples. As an apparatus other than the above, PerkinElmer's NexION350S and Agilent Technologies' Agilent 8900 can also be used.

The ratio of the total content of the first organic compound to the content of the metal component is not particularly limited, but is preferably 0.01 to 10,000, and more preferably 0.1 to 5,000, in terms of superior effects of the present invention.
In addition, the ratio of the total content of the first organic compound and the second organic compound to the content of the metal component is not particularly limited, but in terms of better effects of the present invention, it is preferably 0.01 to 50,000, and more preferably 0.1 to 5,000.
The ratio of the total content of the first organic compound and the second organic compound to the content of the metal particles is not particularly limited, but in terms of superior effects of the present invention, it is preferably 0.01 to 50,000, and more preferably 0.05 to 30,000.
The ratio of the total content of the first organic compound and the second organic compound to the content of the metal ion is not particularly limited, but in terms of superior effects of the present invention, it is preferably 0.03 to 30,000, and more preferably 0.05 to 20,000.

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

The water content in the chemical solution is not particularly limited, but is preferably 0.05 to 2.0% by mass relative to the total mass of the chemical solution. The water content in the chemical solution refers to the water content measured using an apparatus that uses the Karl Fischer water content measurement method as its measurement principle.

<Resin>
The chemical solution may contain a resin.
As the resin, a resin P containing a group (a repeating unit containing an acid-decomposable group) that decomposes under the action of an acid to generate a polar group is more preferable. As the resin, a resin containing a repeating unit represented by the formula (AI) described later, which is a resin whose solubility in a developer mainly composed of an organic solvent decreases under the action of an acid, is more preferable. The resin containing a repeating unit represented by the formula (AI) described later contains a group that decomposes under the action of an acid to generate an alkali-soluble group.
The polar group may be an alkali-soluble group, such as a carboxy group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a phenolic hydroxyl group, or a sulfo group.

In the acid-decomposable group, the polar group is protected by a group that is eliminated by an acid (acid-eliminating group). Examples of the acid-eliminating group include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), and -C(R ₀₁ )(R ₀₂ )(OR ₃₉ ).

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

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

The following is a detailed description of resin P, whose solubility in a developer whose main component is an organic solvent decreases due to the action of acid.

(Formula (AI): Repeating unit containing an acid-decomposable group)
Resin P preferably contains a repeating unit represented by formula (AI).

In formula (AI),
_Xa1 represents a hydrogen atom or an alkyl group which may have a substituent.
T represents a single bond or a divalent linking group.
Ra ₁ to Ra ₃ each independently represent an alkyl group (straight-chain or branched-chain) or a cycloalkyl group (monocyclic or polycyclic).
Two of Ra ₁ to Ra ₃ may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

The content of the repeating unit containing an acid-decomposable group (preferably a repeating unit represented by formula (AI)) is preferably 20 to 90 mol %, more preferably 25 to 85 mol %, and even more preferably 30 to 80 mol %, based on the total repeating units in resin P.

In addition to the repeating unit containing an acid-decomposable group, the resin P may contain other repeating units. Examples of the other repeating units include a repeating unit containing a lactone structure, a repeating unit containing a phenolic hydroxyl group, a repeating unit containing a polar group, and a repeating unit containing a silicon atom in the side chain.

The weight average molecular weight of the resin P is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 5,000 to 15,000, as calculated in terms of polystyrene by gel permeation chromatography (GPC).
The polydispersity (molecular weight distribution) of the resin P is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and even more preferably 1.2 to 2.0.

In the chemical solution, the content of the resin P is preferably 50 to 99.9 mass % of the total solid content, and more preferably 60 to 99.0 mass %.
In addition, in the chemical solution, one type of resin P may be used, or multiple types of resin P may be used.
The solid content means the components in the chemical solution excluding the organic solvent and the solvent such as water.

The chemical solution may further contain known compounds such as an acid generator, a basic compound, a quencher, a hydrophobic resin, and a surfactant.
The chemical solution may contain components contained in the actinic ray-sensitive or radiation-sensitive resin compositions described in, for example, JP 2013-195844 A, JP 2016-057645 A, JP 2015-207006 A, WO 2014/148241 A, JP 2016-188385 A, and JP 2017-219818 A.

<Use of chemicals>
The chemical solution of the present invention is preferably used in the manufacture of semiconductor devices, and in particular, it is preferable to manufacture semiconductor chips using the chemical solution of the present invention.
Specifically, in the manufacturing process of semiconductor devices including a lithography process, an etching process, an ion implantation process, a peeling process, and the like, the liquid is used to treat organic matter after the completion of each process or before moving to the next process, and specifically, is suitably used as a pre-wet liquid, a developing liquid, a rinsing liquid, a polishing liquid, and the like.
In addition, the chemical liquid may be used as a diluting liquid (in other words, a solvent) for the resin contained in the composition for forming a resist film.

Furthermore, the above-mentioned chemical solution can be used for purposes other than the manufacture of semiconductor devices, and can also be used as a developer and rinse solution for polyimide, resist for sensors, resist for lenses, and the like.
The chemical solution can also be used as a solvent for medical or cleaning purposes, for example, for cleaning pipes, containers, and substrates (e.g., wafers, glass, etc.).
As the above-mentioned cleaning application, it is also preferable to use it as a cleaning liquid (pipe cleaning liquid, container cleaning liquid, etc.) for cleaning pipes, containers, etc. that come into contact with liquids such as the pre-wet liquid described above.

Among these, the chemical liquid is preferably used for a pre-wet liquid, a developer, a rinse liquid, a polishing liquid, and a composition for forming a resist film. In particular, when applied to a pre-wet liquid, a developer, and a rinse liquid, it exerts a more excellent effect. It also exerts a more excellent effect when applied to a pipe cleaning liquid used in the pipes used to transport these liquids.

The present invention may be used as a kit containing two or more selected from the group consisting of a pre-wet liquid containing the chemical solution of the present invention, a developer containing the chemical solution of the present invention, a rinse liquid containing the chemical solution of the present invention, a polishing liquid containing the chemical solution of the present invention, and a composition for forming a resist film containing the chemical solution of the present invention.

<Method of manufacturing chemical solution>
The method for producing the above-mentioned chemical solution is not particularly limited, and any known production method can be used. Among them, in terms of obtaining a more excellent effect of the present invention, the method for producing the chemical solution preferably includes a filtration step of filtering the material to be purified containing an organic solvent using a filter to obtain the chemical solution.

The product to be purified used in the filtration process may be procured by purchase or may be obtained by reacting raw materials. It is preferable that the product to be purified has a low impurity content. Examples of commercially available products of such products include those called "high purity grade products."

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

(Filtration process)
The method for producing a drug solution of the present invention preferably includes a filtration step of filtering the target substance using a filter to obtain a drug solution. The method for filtering the target substance using a filter is not particularly limited, but it is preferable to pass the target substance through a filter unit having a housing and a filter cartridge housed in the housing with or without pressure.

- Filter pore size The filter pore size is not particularly limited, and a filter with a pore size that is usually used for filtering the product to be purified can be used. Among them, the filter pore size is preferably 200 nm or less, more preferably 20 nm or less, even more preferably 10 nm or less, particularly preferably 5 nm or less, and most preferably 3 nm or less, in terms of ease of controlling the number of particles (metal particles, etc.) contained in the chemical solution to a desired range. The lower limit is not particularly limited, but generally 1 nm or more is preferred from the viewpoint of productivity.
In this specification, the pore size and pore size distribution of a filter refer to the pore size and pore size distribution determined by the bubble point of isopropanol (IPA) or HFE-7200 ("Novec 7200", manufactured by 3M, hydrofluoroether, C ₄ F ₉ OC ₂ H ₅ ).

It is preferable that the pore size of the filter is 5.0 nm or less, since it is easier to control the number of particles contained in the drug solution. Hereinafter, a filter having a pore size of 5 nm or less is also referred to as a "micropore filter".
The micropore filter may be used alone or together with a filter having another pore size. In particular, it is preferable to use a filter having a larger pore size from the viewpoint of superior productivity. In this case, if the product to be purified, which has been previously filtered through a filter having a larger pore size, is passed through the micropore filter, clogging of the micropore filter can be prevented.
That is, when one filter is used, the pore size of the filter is preferably 5.0 nm or less, and when two or more filters are used, the pore size of the filter having the smallest pore size is preferably 5.0 nm or less.

The form in which two or more filters with different pore sizes are used in sequence is not particularly limited, but includes a method of arranging the filter units already described in sequence along the pipeline through which the product to be purified is transported. In this case, if an attempt is made to keep the flow rate per unit time of the product to be purified constant throughout the entire pipeline, a filter with a smaller pore size may be subjected to greater pressure than a filter with a larger pore size. In this case, it is preferable to arrange a pressure regulating valve and a damper between the filters to keep the pressure on the filter with a smaller pore size constant, or to arrange filter units containing the same filters in parallel along the pipeline to increase the filtration area. In this way, the number of particles in the chemical solution can be controlled more stably.

Filter material The material of the filter is not particularly limited, and known materials can be used as filter materials. Specifically, in the case of a resin, polyamides such as nylon (for example, 6-nylon and 6,6-nylon); polyolefins such as polyethylene and polypropylene; polystyrene; polyimide; polyamideimide; poly(meth)acrylate; polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylenepropene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride; polyvinyl alcohol; polyester; cellulose; cellulose acetate, and the like can be mentioned. Among them, at least one selected from the group consisting of nylon (among which 6,6-nylon is preferred), polyolefins (among which polyethylene is preferred), poly(meth)acrylate, and polyfluorocarbons (among which polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkane (PFA) are preferred.) is preferred, in terms of having better solvent resistance and the resulting chemical solution having better defect suppression performance. These polymers may be used alone or in combination of two or more.
In addition to resin, materials such as diatomaceous earth and glass may also be used.
Alternatively, a polymer (such as nylon graft UPE) obtained by graft copolymerizing polyamide (for example, nylon such as nylon-6 or nylon-6,6) with polyolefin (such as UPE described below) may be used as the material for the filter.

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

Plasma treatment is preferred because it makes the filter surface hydrophilic. There are no particular limitations on the water contact angle on the surface of the filter material that has been hydrophilized by plasma treatment, but the static contact angle at 25°C measured with a contact angle meter is preferably 60° or less, more preferably 50° or less, and even more preferably 30° or less.

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

Examples of ion exchange groups include sulfonic acid groups, carboxy groups, and phosphate groups as cation exchange groups, and quaternary ammonium groups as anion exchange groups. There are no particular limitations on the method for introducing ion exchange groups into a polymer, but examples include a method in which a compound containing an ion exchange group and a polymerizable group is reacted with the polymer to typically perform grafting.

There are no particular limitations on the method for introducing ion exchange groups, but the fibers of the above resins are irradiated with ionizing radiation (alpha rays, beta rays, gamma rays, X-rays, electron beams, etc.) to generate active moieties (radicals) in the resin. The irradiated resin is immersed in a monomer-containing solution to graft polymerize the monomer onto the substrate. As a result, a polymer is generated that is bonded to the polyolefin fibers as a graft-polymerized side chain. The resin containing this generated polymer as a side chain is contacted and reacted with a compound containing an anion exchange group or a cation exchange group, and the ion exchange group is introduced into the graft-polymerized side chain polymer to obtain the final product.

The filter may also be constructed by combining a woven or nonwoven fabric in which ion exchange groups have been formed by radiation graft polymerization with a conventional glass wool, woven or nonwoven filter material.

By using a filter containing an ion exchange group, the content of the metal component (particularly, particles containing metal atoms) in the chemical solution containing the metal component can be easily controlled to a desired range. The material of the filter containing an ion exchange group is not particularly limited, but examples thereof include polyfluorocarbon and a material in which an ion exchange group is introduced into a polyolefin, and a material in which an ion exchange group is introduced into a polyfluorocarbon is more preferable.
The pore size of the filter containing ion exchange groups is not particularly limited, but is preferably 1 to 30 nm, and more preferably 5 to 20 nm. The filter containing ion exchange groups may also serve as the filter having the smallest pore size as described above, or may be used separately from the filter having the smallest pore size. Among these, in terms of obtaining a more excellent effect of the present invention, the filtration step preferably uses a filter containing ion exchange groups and a filter having no ion exchange groups and having the smallest pore size.
The material of the filter having the minimum pore size already described is not particularly limited, but from the viewpoint of solvent resistance and the like, generally, at least one selected from the group consisting of polyfluorocarbons and polyolefins is preferred, and polyolefins are more preferred.

Therefore, the filters used in the filtration process may be made of two or more different materials, for example, two or more filters selected from the group consisting of polyolefins, polyfluorocarbons, polyamides, and filters made of these materials with ion exchange groups introduced therein.

-Pore structure of the filter The pore structure of the filter is not particularly limited and may be appropriately selected depending on the components in the product to be purified. In this specification, the pore structure of the filter means the pore size distribution, the positional distribution of the pores in the filter, the shape of the pores, etc., and can typically be controlled by the manufacturing method of the filter.
For example, porous membranes can be obtained by sintering powders of resins or the like, and fibrous membranes can be obtained by electrospinning, electroblowing, meltblowing, and other methods, each of which has a different pore structure.

"Porous membrane" means a membrane that retains components of the product to be purified, such as gels, particles, colloids, cells, and poly-oligomers, but allows components substantially smaller than the pores to pass through the pores. Retention of components of the product by a porous membrane may depend on operating conditions, such as face velocity, use of surfactants, pH, and combinations thereof, and may depend on the pore size, structure of the porous membrane, and the size and structure of the particles to be removed (e.g., hard particles or gels).

When the product to be purified contains negatively charged particles, polyamide filters act as non-sieving membranes to remove such particles. Exemplary non-sieving membranes include, but are not limited to, nylon membranes such as nylon-6 membranes and nylon-6,6 membranes.
It is noted that, as used herein, "non-sieving" retention mechanisms refer to retention that occurs due to mechanisms such as obstruction, diffusion and adsorption that are not related to the pressure drop or pore size of the filter.

Non-sieving retention includes retention mechanisms such as obstruction, diffusion, and adsorption that remove target particles in the product, regardless of the pressure drop across the filter or the pore size of the filter. Particle adsorption to the filter surface can be mediated, for example, by intermolecular van der Waals and electrostatic forces. Obstruction effects occur when particles moving through a non-sieving membrane layer with a tortuous path cannot be redirected quickly enough to avoid contact with the non-sieving membrane. Particle transport by diffusion results primarily from random or Brownian motion of small particles, which creates a certain probability of the particle colliding with the filter media. Non-sieving retention mechanisms can be active when there are no repulsive forces between the particle and the filter.

UPE (ultra-high molecular weight polyethylene) filters are typically sieving membranes, which refers to membranes that capture particles primarily through a sieving retention mechanism or that are optimized for capturing particles through a sieving retention mechanism.
Typical examples of sieving membranes include, but are not limited to, polytetrafluoroethylene (PTFE) membranes and UPE membranes.
The "sieve retention mechanism" refers to the retention of particles that are larger than the pore size of the porous membrane. Sieve retention is improved by forming a filter cake (an agglomeration of particles to be removed on the membrane surface). The filter cake effectively performs the function of a secondary filter.

The material of the fiber membrane is not particularly limited as long as it is a polymer capable of forming a fiber membrane. Examples of the polymer include polyamides. Examples of the polyamide include nylon 6 and nylon 6,6. The polymer forming the fiber membrane may be poly(ethersulfone). When the fiber membrane is on the primary side of the porous membrane, it is preferable that the surface energy of the fiber membrane is higher than that of the polymer that is the material of the porous membrane on the secondary side. An example of such a combination is when the fiber membrane is made of nylon and the porous membrane is made of polyethylene (UPE).

The method for producing the fiber membrane is not particularly limited, and any known method can be used. As described above, examples of the method for producing the fiber membrane include electrospinning, electroblowing, and meltblowing.

The pore structure of the porous membrane (e.g., porous membranes containing UPE, PTFE, etc.) is not particularly limited, but examples of the pore shape include lace-like, string-like, and node-like.
The distribution of the pore sizes in the porous membrane and the distribution of the positions in the membrane are not particularly limited. The size distribution may be smaller and the distribution positions in the membrane may be symmetric. The size distribution may be larger and the distribution positions in the membrane may be asymmetric (the above membrane is also called "asymmetric porous membrane"). In an asymmetric porous membrane, the size of the pores changes in the membrane, and typically the pore size increases from one surface of the membrane to the other surface of the membrane. In this case, the surface on the side where there are more pores with large pore sizes is called the "open side", and the surface on the side where there are more pores with small pore sizes is also called the "tight side".
Asymmetric porous membranes include, for example, membranes in which the pore size is smallest at some point within the thickness of the membrane (also called "hourglass shaped").

By using an asymmetric porous membrane with larger pore size on the primary side, in other words the primary side being open, a pre-filtration effect can be created.

The porous membrane may include a thermoplastic polymer such as PESU (polyethersulfone), PFA (perfluoroalkoxyalkane, a copolymer of tetrafluoroethylene and perfluoroalkoxyalkane), polyamide, and polyolefin, or may include polytetrafluoroethylene, etc.
Among them, the material of the porous membrane is preferably ultra-high molecular weight polyethylene, which means a thermoplastic polyethylene having an extremely long chain and has a molecular weight of at least one million, typically 2 to 6 million.

The filters used in the filtration process may be two or more types of filters with different pore structures, or a porous membrane filter and a fiber membrane filter may be used in combination. A specific example is a method using a nylon fiber membrane filter and a UPE porous membrane filter.

The filter may be commercially available as described above. When such a filter is put into distribution, the filter is often packaged in a packaging material, such as being placed in a packaging bag and sealed in order to prevent contamination. In this case, when the part of the packaging material that may come into contact with the filter (contact part) is polyolefin (polyethylene including high density polyethylene, etc.), impurities are more likely to adhere to the filter, causing contamination, compared to when the contact part is a fluororesin or stainless steel.
For this reason, it is preferable that the filter is packed in a packing material in which at least a part of the portion that comes into contact with the filter is made of a fluororesin or stainless steel.

The fluororesin in the contact portion may be, for example, PTFE or PFA.
The stainless steel in the contact portion may be any of the corrosion-resistant materials described below, and among these, it is preferable that the contact portion be made of electrolytically polished stainless steel (EP-SUS).
The area of the contact portion which is the fluororesin and/or stainless steel is preferably 50 to 100%, more preferably 90 to 100%, and even more preferably 99 to 100%, of the total area of the contact portion.
The form of the packaging material is not particularly limited, and may be in the form of a bag or a capsule.
The packaging material may be made of fluororesin and/or stainless steel in its entirety, or may be a composite material with other materials, as long as at least a part of the contact portion is made of fluororesin and/or stainless steel. For example, the packaging material may be a composite material with a layer structure in which the contact portion is made of fluororesin and/or stainless steel and the portion other than the contact portion is made of fluororesin and/or stainless steel.

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

As described above, the filtration step according to the embodiment of the present invention may be a multistage filtration step in which the material to be purified is passed through two or more types of filters that are different in at least one aspect selected from the group consisting of the filter material, pore size, and pore structure.
The material to be purified may be passed through the same filter multiple times, or through multiple filters of the same type.

The material of the liquid-contacting part of the refining device used in the filtration process (meaning the inner wall surface that may come into contact with the product to be refined and the chemical liquid) is not particularly limited, but is preferably made of at least one material selected from the group consisting of non-metallic materials (such as fluororesins) and electrolytically polished metallic materials (such as stainless steel) (hereinafter, these are collectively referred to as "corrosion-resistant materials"). For example, when the liquid-contacting part of the production tank is made of a corrosion-resistant material, it can be meant that the production tank itself is made of a corrosion-resistant material, or the inner wall surface of the production tank is coated with a corrosion-resistant material.

The non-metallic material is not particularly limited, and any known material can be used.
Examples of non-metallic materials include, but are not limited to, at least one selected from the group consisting of polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, and fluorine-based resin (e.g., tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene-ethylene copolymer resin, trifluorochloroethylene-ethylene copolymer resin, vinylidene fluoride resin, trifluorochloroethylene copolymer resin, and vinyl fluoride resin).

The metal material is not particularly limited, and any known material can be used.
The metal material may be, for example, a metal material having a total content of chromium and nickel of more than 25 mass% based on the total mass of the metal material, and more preferably 30 mass% or more. The upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but is generally preferably 90 mass% or less.
Examples of metallic materials include stainless steel and nickel-chromium alloys.

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

The nickel-chromium alloy is not particularly limited, and any known nickel-chromium alloy can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75 mass % and a chromium content of 1 to 30 mass % is preferable.
Examples of nickel-chromium alloys include Hastelloy (trade name, the same applies below), Monel (trade name, the same applies below), and Inconel (trade name, the same applies below), etc. More specifically, examples include Hastelloy C-276 (Ni content 63 mass%, Cr content 16 mass%), Hastelloy-C (Ni content 60 mass%, Cr content 17 mass%), and Hastelloy C-22 (Ni content 61 mass%, Cr content 22 mass%), etc.
Furthermore, the nickel-chromium alloy may further contain boron, silicon, tungsten, molybdenum, copper, cobalt, and the like, in addition to the above-mentioned alloy, as required.

There are no particular limitations on the method for electrolytically polishing the metal material, and any known method can be used. For example, the methods described in paragraphs [0011] to [0014] of JP 2015-227501 A and paragraphs [0036] to [0042] of JP 2008-264929 A can be used.

It is presumed that the chromium content in the surface passive layer of a metal material is higher than the chromium content in the parent phase due to electrolytic polishing, and therefore, it is presumed that the use of a refining device whose liquid-contacting parts are made of electrolytically polished metal material makes it difficult for metal components to leak into the product being refined.
The metal material may be buffed. The method of buffing is not particularly limited, and known methods can be used. The size of the polishing grains used for finishing the buffing is not particularly limited, but #400 or less is preferable because it tends to reduce the unevenness of the surface of the metal material. The buffing is preferably performed before the electrolytic polishing.

(Other processes)
The method for producing the chemical solution may further include a step other than the filtration step, such as a distillation step, a reaction step, and a static electricity removal step.

(Distillation process)
The distillation step is a step of distilling a purification target material containing an organic solvent to obtain a distilled purification target material. The method of distilling the purification target material is not particularly limited, and a known method can be used. A typical example is a method in which a distillation column is disposed on the primary side of a purification apparatus subjected to a filtration step, and the distilled purification target material is introduced into a production tank.
In this case, the liquid-contacting parts of the distillation column are not particularly limited, but are preferably made of the corrosion-resistant materials already explained.

(Reaction step)
The reaction step is a step of reacting the raw materials to produce a product to be purified that contains the organic solvent as a reactant. The method of producing the product to be purified is not particularly limited, and any known method can be used. Typically, a reaction tank is disposed on the primary side of a production tank (or a distillation column) of a purification apparatus to be subjected to a filtration step, and the reactant is introduced into the production tank (or the distillation column).
In this case, the liquid-contacting parts of the production tank are not particularly limited, but are preferably made of the corrosion-resistant materials already described.

(Static charge removal process)
The charge removal step is a step of removing static electricity from the material to be purified to reduce the charged potential of the material to be purified.
The method for removing static electricity is not particularly limited, and any known method can be used. For example, the method for removing static electricity includes contacting the product to be purified with a conductive material.
The contact time for contacting the material to be purified with the conductive material is preferably 0.001 to 60 seconds, more preferably 0.001 to 1 second, and even more preferably 0.01 to 0.1 seconds. Examples of the conductive material include stainless steel, gold, platinum, diamond, and glassy carbon.
As a method for contacting the material to be purified with a conductive material, for example, a grounded mesh made of a conductive material is placed inside the pipeline and the material to be purified is passed through the mesh.

It is preferable that the purification of the target substance, as well as the associated processes such as opening containers, cleaning containers and equipment, storing solutions, and analysis, are all carried out in a clean room. The clean room is preferably a clean room with a cleanliness level of class 4 or higher as defined by the international standard ISO14644-1:2015 established by the International Organization for Standardization. Specifically, it is preferable that the clean room meets any of ISO class 1, ISO class 2, ISO class 3, and ISO class 4, more preferably ISO class 1 or ISO class 2, and even more preferably ISO class 1.

There are no particular limitations on the storage temperature of the drug solution, but a storage temperature of 4°C or higher is preferred, as this makes it more difficult for trace amounts of impurities contained in the drug solution to be eluted, resulting in a more excellent effect of the present invention.

<Drug Solution Container>
The drug solution produced by the above purification method may be stored in a container until it is used.
Such a container and the liquid medicine contained therein are collectively referred to as a liquid medicine container. The liquid medicine is taken out of the stored liquid medicine container and used.

The container for storing the above-mentioned chemical solution is preferably one that is highly clean inside and has little elution of impurities for use in semiconductor device manufacturing.
Specific examples of containers that can be used include the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd., but are not limited to these.

As a container, it is also preferable to use a multi-layer bottle whose inner wall has a six-layer structure made of six types of resin, or a multi-layer bottle whose inner wall has a seven-layer structure made of six types of resin, in order to prevent impurities from being mixed in (contaminated) with the liquid medicine. Examples of such containers include the containers described in JP 2015-123351 A.

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

The porosity within the container of the drug solution container is preferably 2 to 80% by volume, more preferably 2 to 50% by volume, and even more preferably 5 to 30% by volume.
The porosity is calculated according to formula (1).
Equation (1): Porosity = {1 - (volume of drug solution in container / volume of container)} x 100
The container volume is synonymous with the internal volume (capacity) of the container.
By setting the porosity within this range, it is possible to ensure storage stability by limiting contamination such as impurities.

The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, processing contents, and processing procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

In addition, when preparing the chemical solutions in the examples and comparative examples, handling of containers, preparation of the chemical solutions, filling, storage, and analytical measurements were all carried out in a clean room that met ISO class 2 or 1 standards.

(filter)
The following filters were used:
Filter A: Activated carbon filter "FCC-S" (fiber) from Nippon Filter Co., Ltd.
"Purasol 200 nm": UPE membrane (material) manufactured by Entegris, pore size 200 nm
"PTFE 7 nm": polytetrafluoroethylene filter, manufactured by Entegris, pore size 7 nm
"UPE 1 nm": ultra-high molecular weight polyethylene filter, manufactured by Pall, pore size 1 nm
"UPE 3nm": Ultra-high molecular weight polyethylene filter, manufactured by Pall, pore size 3nm
"UPE 5nm": Ultra-high molecular weight polyethylene filter, manufactured by Pall, pore size 5nm
"Nylon 5 nm": Nylon filter, manufactured by Pall, pore size 5 nm

<Product to be purified>
In order to produce the chemical solutions of the Examples and Comparative Examples, the following organic solvents were used as materials to be purified.
PGMM: Propylene glycol monomethyl ether PGME: Propylene glycol monoethyl ether PGMP: Propylene glycol monopropyl ether PGMEA: Propylene glycol monomethyl ether acetate (Note that "PGMEA (A)" to "PGMEA (D)" in the table represent four types of PGMEA obtained from different companies.)
EL: Ethyl lactate MPM: Methyl methoxypropionate CyPn: Cyclopentanone CyHe: Cyclohexanone (Note that "CyHe", "CyHe (A)" to "CyHe (D)" in the table represent five types of CyHe obtained from different companies.)
γBL: butyrolactone DIAE: diisoamyl ether MIBC: 4-methyl-2-pentanol (Note that “MIBC”, “MIBC (A)” to “MIBC (D)” in the table represent five types of MIBC obtained from different companies.)
IPA: Isopropanol DMSO: Dimethylsulfoxide NMP: N-Methylpyrrolidone DEG: Diethylene glycol EG: Ethylene glycol DPG: Dipropylene glycol PG: Propylene glycol PC: Propylene carbonate Sulfolane: Sulfolane 2-Heptanone: 2-Heptanone nBA: Butyl acetate (Note that "nBA (A)" to "nBA (D)" in the table represent four types of nBA obtained from different companies.)
iAA: isoamyl acetate, butyl butyrate, isobutyl isobutyrate, isoamyl ether (2.1)
Undecane dimethyl malonate (10.3)
The values in parentheses are the distances (MPa ^0.5 ) between the Hansen solubility parameters of isoamyl ether and dimethyl malonate relative to eicosene.

<Container>
The following containers were used to store the drug solutions:
・EP-SUS: Container with electrolytically polished stainless steel in contact with liquid ・PFA: Container with perfluoroalkoxyalkane-coated in contact with liquid

Purification Procedure
One of the above-mentioned substances to be purified was selected and subjected to the distillation purification treatment shown in Table 1.
In the table, "Yes-1" in the "Distillation purification" column indicates that atmospheric distillation was performed using a distillation tower (theoretical number of plates: 15 plates), "Yes-2" indicates that vacuum distillation was performed using a distillation tower (theoretical number of plates: 25 plates), "Yes-3" indicates that vacuum distillation was performed twice using a distillation tower (theoretical number of plates: 30 plates), "Yes-4" indicates that atmospheric distillation was performed using a distillation tower (theoretical number of plates: 20 plates), "Yes-5" indicates that atmospheric distillation was performed using a distillation tower (theoretical number of plates: 10 plates), and "Yes-6" indicates that atmospheric distillation was performed using a distillation tower (theoretical number of plates: 8 plates).
However, in the table, "No" in the "Distillation purification" column indicates that distillation treatment was not carried out, and in the examples where the "Distillation purification" column has "No", distillation purification was not carried out.

Next, the distilled and purified product was stored in a storage tank, and the product stored in the storage tank was filtered through filters 1 and 2 shown in Table 1. The product after filtration through filter 2 was circulated upstream of filter 1 and filtered again through filters 1 and 2, thereby carrying out a circulating filtration process.
Next, the purified product that had been subjected to the circulating filtration treatment using filters 1 and 2 was passed through filters 3 and 4 shown in Table 1 in this order, and stored in a storage tank.
Next, the product to be purified stored in the storage tank was filtered using filter 5 described in Table 1, and the product to be purified after filtration using filter 5 was circulated to the upstream side of filter 5 and filtered again using filter 5, thereby carrying out a circulating filtration process.
After the circulation filtration treatment, the mixture was placed in a container shown in Table 1 with a predetermined void ratio.

In addition, during the series of purification processes described above, the liquid-contacting parts of the various devices that come into contact with the purified product (e.g., distillation columns, piping, storage tanks, etc.) were made of electrolytically polished stainless steel.

The organic and metal content of the chemical solution was measured using the method described below.

<Organic ingredient content>
The contents of organic components (first organic compound, second organic compound, etc.) in various chemical solutions were analyzed using a gas chromatography mass spectrometry (GC/MS) device (manufactured by Agilent, GC: 7890B, MS: 5977B EI/CI MSD).

<Metal Component Content>
The content of metal components (metal ions, metal particles) in the chemical solution was measured by a method using ICP-MS and SP-ICP-MS.
The following equipment was used:
Manufacturer: PerkinElmer
Model: NexION350S
The following analysis software was used:
・Syngistix Nano Application Module for "SP-ICP-MS" ・Syngistix for ICP-MS Software

In the table, "ClogP" represents the ClogP value of the organic solvent.
"Purity" in the table indicates the content (mass %) of the organic solvent in the obtained chemical solution relative to the total mass of the chemical solution.
In the table, "Total content 1 (ppt by mass)" represents the total content (ppt by mass) of the first organic compound, and "Total content 2 (ppt by mass)" represents the total content (ppt by mass) of the second organic compound.
In the table, "Ratio 1" represents the ratio of the total content of the first organic compound to the content of the metal component, "Ratio 2" represents the ratio of the total content of the first organic compound and the second organic compound to the content of metal particles, "Ratio 3" represents the ratio of the total content of the first organic compound and the second organic compound to the content of metal ions, "Ratio 4" represents the ratio of the total content of the first organic compound and the second organic compound to the content of the metal component, and "Ratio 5" represents the ratio of the total content of the first organic compound and the second organic compound other than compound (VI) to the content of compound (VI).
The "void ratio" column in the table indicates the value calculated by formula (X).
Formula (X): Porosity = {1 - (volume of drug solution in container / volume of container)} x 100

The thus obtained drug solution contained the compounds shown in the columns "Compound (I)" to "Compound (VII)".
In the "Compound (I)" to "Compound (VII)" columns in the table, the "Type" column indicates each compound as follows.
The ClogP values of the compounds described below were as follows:
Compound 5: ClogP 6.20
Compound 6: ClogP 8.87
Compound 7: ClogP -2.0 to 5.0
Compound 8: ClogP -3.0 to 1.0
Compound 9: ClogP -3.0 to 1.0
Compound 10: ClogP 0-4.0
Compound 11: ClogP 0-8.0
Compound 12: ClogP -0.15
Compound 13: ClogP 2.25
Compound 14: ClogP 4.0-6.0
Compound 15: ClogP 18.89
Compound 16: ClogP 4.0-8.0
Compound 17: ClogP 4.0-8.0
Compound 18: ClogP 7.36
Compound 19: ClogP 8.71
Compound 20: ClogP 4.82
Compound 21: ClogP 8.01
Compound 22: ClogP 5.00
Compound 24: ClogP 5.0-8.5
Compound 25: ClogP 5.0-8.5
Compound 26: ClogP 3.0-4.5
Compound 27: ClogP 0.78
Compound 28: ClogP 8.23
Compound 29: ClogP 14.23
Compound 30: ClogP 4.1
Compound 31: ClogP 2.7
Compound 32: ClogP 0.48
Compound 33: ClogP 4.26
Compound 35: ClogP 6.92
Compound 36: ClogP 4.34
Compound 37: ClogP 3.64

The * in _L1 in Compound 8 and Compound 9 indicates the bonding position.

<Test>
[Pre-wet liquid, rinsing liquid]
The prepared chemical solutions were evaluated for their defect suppression properties when used as a pre-wet solution and a rinsing solution by the method described below.
First, the chemical solutions were spin-discharged onto a silicon substrate having a diameter of 300 mm, and 0.5 cc of each chemical solution was discharged onto the surface of the substrate while the substrate was rotating. The substrate was then spin-dried. Next, using a wafer inspection device "SP-5" manufactured by KLA-Tencor Corporation, the number of defects present on the substrate after the chemical solutions were applied was counted (this was taken as the measurement value).
Next, using EDAX (energy-dispersive X-ray spectroscopy), particulate foreign matter among the defects on this wafer was classified into "metal residue defects" mainly composed of metal and "particulate organic residue defects" mainly composed of organic matter, and each was measured. Furthermore, non-particulate stain-like defects were counted as "stain-like defects."
In addition, if the evaluation of metal residue defects, particulate organic residue defects, and stain-like residue defects is a rating of C or higher, the chemical solution has the defect suppression properties required of the chemical solution.

<Individual evaluation (metal residue defects, particulate organic residue defects, stain-like residue defects)>
A: The corresponding number of defects was 20 or less per wafer.
B: The corresponding number of defects was greater than 20/wafer and less than or equal to 50/wafer.
C: The corresponding number of defects was greater than 50/wafer and less than or equal to 100/wafer.
D: The number of corresponding defects exceeded 100/wafer.

[Developer]
The prepared chemical solutions were evaluated for their defect suppression ability when used as developers by the method described below.
First, a resist pattern was formed by the following procedure.
An organic anti-reflective coating composition ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied to a silicon substrate having a diameter of 300 mm and baked at 205° C. for 60 seconds to form an anti-reflective coating having a thickness of 78 nm.
To improve the coatability, a pre-wetting liquid (CyHe in Example 30 was used) was dropped onto the surface of the silicon wafer on which the anti-reflective coating was formed, on the side of the anti-reflective coating, and spin coating was carried out.
Next, (actinic ray-sensitive or radiation-sensitive resin composition 1) or (actinic ray-sensitive or radiation-sensitive resin composition 2) described below was applied onto the antireflective film after the prewetting process, and prebaked (PB) at 100° C. for 60 seconds to form a resist film with a thickness of 150 nm.
In Examples 49 to 59 and Comparative Examples 3 and 4, (actinic ray-sensitive or radiation-sensitive resin composition 1) was used, and in Examples 60 to 70, (actinic ray-sensitive or radiation-sensitive resin composition 2) was used.

(Actinic ray- or radiation-sensitive resin composition 1)
Acid-decomposable resin (resin represented by the following formula (weight average molecular weight (Mw): 7500); the numerical values shown for each repeating unit represent mol %): 100 parts by mass

Photoacid generator as shown below: 8 parts by weight

Quencher shown below: 5 parts by weight (mass ratio, from left to right, was 0.1:0.3:0.3:0.2). Of the quenchers shown below, the polymer type quencher has a weight average molecular weight (Mw) of 5000. The numerical values listed for each repeating unit indicate the molar ratio.

Hydrophobic resin as shown below: 4 parts by weight (the mass ratio, from left to right, was 0.5:0.5). Note that of the hydrophobic resins shown below, the hydrophobic resin on the left has a weight average molecular weight (Mw) of 7000, and the hydrophobic resin on the right has a weight average molecular weight (Mw) of 8000. Note that in each hydrophobic resin, the numerical value listed for each repeating unit indicates the molar ratio.

solvent:
PGMEA (propylene glycol monomethyl ether acetate): 3 parts by mass Cyclohexanone: 600 parts by mass γ-BL (γ-butyrolactone): 100 parts by mass

(Actinic ray- or radiation-sensitive resin composition 2)
Acid-decomposable resin (resin represented by the following formula (weight average molecular weight (Mw): 8000)): 100 parts by mass

In addition, the content of each repeating unit in the above formula was, from left to right, 30 mol%, 15 mol%, 15 mol%, 20 mol%, and 20 mol% relative to the total repeating units.

Photoacid generator as shown below: 15 parts by weight

Quencher as shown below: 7 parts by weight (mass ratio, from left to right, was 1:1)

Hydrophobic resin shown below: 20 parts by mass (the mass ratio, from top to bottom, was 3:7)
Among the hydrophobic resins shown below, the hydrophobic resin in the upper row has a weight average molecular weight (Mw) of 10,000, and the hydrophobic resin in the lower row has a weight average molecular weight (Mw) of 7,000. In the hydrophobic resins shown in the lower row, the numerical values given for each repeating unit indicate the molar ratio.

solvent:
PGMEA (propylene glycol monomethyl ether acetate): 50 parts by mass PGME (propylene glycol monomethyl ether): 100 parts by mass 2-heptanone: 100 parts by mass γ-BL (γ-butyrolactone): 500 parts by mass

The wafer on which the resist film was formed was subjected to pattern exposure at 25 mJ/ ^cm2 using an ArF excimer laser scanner (Numerical Aperture: 0.75). Then, it was heated at 120°C for 60 seconds. Then, it was paddled with each developer (chemical solution) for 30 seconds and developed. Then, the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds to form a negative resist pattern. Then, the obtained negative pattern was heated at 200°C for 300 seconds. Through the above process, an L/S pattern (average pattern width: 45 nm) with a line/space of 1:1 was obtained. Evaluation of developability and defect suppression was performed for each pattern.

<Defect suppression>
The formed wafer patterns were observed using a pattern defect measurement device (Hitachi High-Technologies Corporation's Multipurpose SEM (Scanning Electron Microscope) "Inspago" RS6000 series) and the number of the following defects was measured.
- Development defect: a defect in which a space is not formed all the way to the bottom of the pattern - Residue defect: a defect in which foreign matter is present on the pattern - Uniformity defect: a defect in which the pattern width is more than ±1 nm from the specified value If the evaluation of development defect, residue defect, and uniformity defect is all rated C or higher, the chemical solution contains the defect suppression properties required of the chemical solution.

<Individual evaluation (development failure, residue defect, uniformity defect)>
AA: The corresponding defect count was 3 or less per wafer.
A: The corresponding number of defects was greater than 3/wafer and less than or equal to 5/wafer.
B: The corresponding number of defects was greater than 5/wafer and less than or equal to 10/wafer.
C: The corresponding number of defects was greater than 10/wafer and less than or equal to 30/wafer.
D: The corresponding number of defects exceeded 30/wafer.

In Table 1, "Application 1" means that the above test was conducted using the chemical solution described in each Example and Comparative Example as a pre-wet solution and a rinse solution. "Application 2" means that the above test was conducted using the chemical solution described in each Example and Comparative Example as a developer. In Example 75, dimethyl malonate and isoamyl ether were mixed in a ratio of 5:5 (by mass).

In Table 1, data for each Example and Comparative Example are shown in each row of Table 1 [Part 1] <1> to <7> and Table 1 [Part 2] <1> to <7>. For example, in Example 1, as shown in Table 1 [Part 1] <1>, PGMM is used as an organic solvent, as shown in Table 1 [Part 1] <2>, the total amount of metal ions in the chemical solution is 35 mass ppt, as shown in Table 1 [Part 1] <3>, the total amount of metal particles in the chemical solution is 12.3 mass ppt, as shown in Table 1 [Part 1] <4>, the total amount of compound (I) is 89 mass ppt, as shown in Table 1 [Part 1] <5>, the total amount of compound (V) is 45 mass ppt, as shown in Table 1 [Part 1] <6>, the ratio 1 is 2.12, and as shown in Table 1 [Part 1] <7>, the metal residue is "A". The same applies to the other Examples and Comparative Examples.

From the results shown in the table, it was confirmed that the chemical solution of the present invention has excellent defect suppression properties when applied to the manufacture of semiconductor devices.
In particular, when comparing Examples 23, 24, 32, 33, 41, 42, and other Examples, the effect was more excellent when the content of the metal component was 0.1 to 500 ppt by mass relative to the total mass of the chemical solution.
Furthermore, a comparison of Examples 26, 35, 44, and other Examples showed that the effect was better when the total content 1 (total content of the first organic compounds) was 10,000 ppt by mass or less (preferably, 2,000 ppt by mass or less).
In addition, a comparison of Examples 23, 25, and other Examples showed that when the ratio 1 (the ratio of the total content of the first organic compound to the content of the metal component) was 0.01 to 10,000, the effect was more excellent.

<EUV Exposure>
(Actinic ray- or radiation-sensitive resin composition (resist composition 1))
First, resist composition 1 was obtained by mixing the components in the following ratio.
Resin (A-1): 0.77 g
Photoacid generator (B-1): 0.03 g
Basic compound (E-3): 0.03 g
PGMEA (commercially available, high purity grade): 67.5 g
Ethyl lactate (commercially available, high purity grade): 75g

Resin (A-1)
As the resin (A-1), the following resin was used.

Photoacid generator (B-1)
As the photoacid generator (B-1), the following compound was used.

Basic compound (E-3)
As the basic compound (E-3), the following compound was used.

(Pattern formation and evaluation)
First, AL412 (manufactured by Brewer Science) was applied onto a silicon wafer with a diameter of 300 mm, and baked at 200° C. for 60 seconds to form a resist underlayer film with a thickness of 20 nm. A pre-wet liquid (cyclohexanone/manufactured by FFUS) was applied thereon, and a resist composition was applied thereon, followed by baking (PB: Prebake) at 100° C. for 60 seconds to form a resist film with a thickness of 30 nm.

This resist film was exposed through a reflective mask using an EUV exposure machine (manufactured by ASML; NXE3350, NA 0.33, Dipole 90°, outer sigma 0.87, inner sigma 0.35). Then, it was heated at 85° C. for 60 seconds (PEB: Post Exposure Bake). Next, a developer (butyl acetate/manufactured by FETW) was sprayed for 30 seconds by the spray method to develop, and a rinse solution was discharged onto the silicon wafer for 20 seconds by the spin coating method to rinse. Next, the silicon wafer was rotated at a rotation speed of 2000 rpm for 40 seconds to form a line-and-space pattern with a space width of 20 nm and a pattern line width of 15 nm.
The rinsing liquid used was the same as the chemical liquid used in the above-mentioned Examples 1 to 48 and 71 to 75. When the above-mentioned metal residue defects, particulate organic residue defects, and stain-like residue defects were evaluated, the desired effects were obtained with the same tendency as in Table 1 [Part 1] <7>.

Claims (19)

A chemical liquid containing an organic solvent and used as a pre-wet liquid or a rinse liquid,
The organic solvent contains only cyclohexanone,
Contains at least one first organic compound selected from the group consisting of compounds represented by general formulas (I) to (III),
the first organic compound comprises one or more compounds selected from the group consisting of compound 35, compound 36, and compound 37;
The total content of the first organic compound is 1 to 10,000 ppt by mass relative to the total mass of the chemical solution;
Further, the composition contains at least one second organic compound selected from the group consisting of compounds represented by general formulas (IV) to (VII),
The total content of the second organic compounds is 1 ppt by mass or more and 100,000 ppt by mass or less with respect to the total mass of the chemical solution.
In formula (I), Y represents a benzene ring group which may be substituted with an alkyl group, or a group represented by formula (A).
When Y represents a benzene ring group, s represents 1, L represents a single bond, and R ^1a represents an alkyl group which may contain a substituent. The alkyl group may contain a heteroatom. When the benzene ring group is substituted with an alkyl group, the alkyl group and R ^1a may be bonded to each other to form a ring. When the benzene ring group is substituted with a plurality of alkyl groups, the alkyl groups may be bonded to each other to form a ring.
When Y represents a group represented by formula (A), s represents 3, L represents a methylene group, and each R ^1a independently represents an alkyl group.
In formula (II), R ^2a to R ^2h each independently represent an alkyl group which may contain a substituent.
R ^2b and R ^2e may be bonded to each other to form a ring.
The group formed by combining R ^2b and R ^2e with each other is —O—(—Si(R ²ⁱ ) ₂ —O—) _a —.
a represents an integer of 1 or more.
R ²ⁱ represents an alkyl group which may contain a substituent.
A plurality of R ^2i's may be the same or different.
In formula (III), R ^3a represents -N(R ^3c )R ^3d or -SR ^3e .
R ^3c , R ^3d and R ^3e each represent a hydrogen atom or a substituent.
R ^3b represents -NH- or -S-.
In the general formula (IV), X represents a benzene ring group which may contain a substituent, a cyclohexene ring group which may contain a substituent, or a cyclohexane ring group which contains a cycloalkyloxy group as a substituent. The cyclohexane ring group may further contain another substituent.
In formula (V), R ^5a represents an alkyl group which may contain a substituent, or a hydrogen atom.
R ^5b and R ^5c each independently represent a hydrogen atom, -AL-O-R ^5d , -CO-R ^5e , or -CH(OH)-R ^5f .
AL represents an alkylene group which may contain a substituent.
R ^5d , R ^5e and R ^5f each independently represent a substituent.
When a plurality of R ^5d are present, the plurality of R ^5d may be the same or different. When a plurality of R ^6e are present, the plurality of R ^5e may be the same or different. When a plurality of R ^5f are present, the plurality of R ^5f may be the same or different.
A combination of two selected from the group consisting of a substituent which the alkyl group represented by ^R5a may have, ^R5d , R5e, and ^R5f , two ^R5d 's, two ^R5e 's, or two ^{R5f 's} may be bonded to each other to form a ring.
At least one of R ^5a , R ^5b and R ^5c is other than a hydrogen atom.
In formula (VI), R ^6a and R ^6b each independently represent an alkyl group which may contain a substituent.
In formula (VII), R ^7a to R ^7c each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a benzene ring group which may have a substituent. A chemical liquid containing an organic solvent and used as a pre-wet liquid or a rinse liquid,
The organic solvent contains only propylene glycol monomethyl ether acetate,
Contains at least one first organic compound selected from the group consisting of compounds represented by general formulas (I) to (III),
the first organic compound comprises compound 23;
The total content of the first organic compound is 12 to 2113 ppt by mass relative to the total mass of the chemical solution;
Further, the composition contains at least one second organic compound selected from the group consisting of compounds represented by general formulas (IV) to (VII),
The total content of the second organic compounds is 1 ppt by mass or more and 100,000 ppt by mass or less with respect to the total mass of the chemical solution.
In formula (I), Y represents a benzene ring group which may be substituted with an alkyl group, or a group represented by formula (A).
When Y represents a benzene ring group, s represents 1, L represents a single bond, and R ^1a represents an alkyl group which may contain a substituent. The alkyl group may contain a heteroatom. When the benzene ring group is substituted with an alkyl group, the alkyl group and R ^1a may be bonded to each other to form a ring. When the benzene ring group is substituted with a plurality of alkyl groups, the alkyl groups may be bonded to each other to form a ring.
When Y represents a group represented by formula (A), s represents 3, L represents a methylene group, and each R ^1a independently represents an alkyl group.
In formula (II), R ^2a to R ^2h each independently represent an alkyl group which may contain a substituent.
R ^2b and R ^2e may be bonded to each other to form a ring.
The group formed by combining R ^2b and R ^2e with each other is —O—(—Si(R ²ⁱ ) ₂ —O—) _a —.
a represents an integer of 1 or more.
R ²ⁱ represents an alkyl group which may contain a substituent.
A plurality of R ^2i's may be the same or different.
In formula (III), R ^3a represents -N(R ^3c )R ^3d or -SR ^3e .
R ^3c , R ^3d and R ^3e each represent a hydrogen atom or a substituent.
R ^3b represents -NH- or -S-.
In the general formula (IV), X represents a benzene ring group which may contain a substituent, a cyclohexene ring group which may contain a substituent, or a cyclohexane ring group which contains a cycloalkyloxy group as a substituent. The cyclohexane ring group may further contain another substituent.
In formula (V), R ^5a represents an alkyl group which may contain a substituent, or a hydrogen atom.
R ^5b and R ^5c each independently represent a hydrogen atom, -AL-O-R ^5d , -CO-R ^5e , or -CH(OH)-R ^5f .
AL represents an alkylene group which may contain a substituent.
R ^5d , R ^5e and R ^5f each independently represent a substituent.
When a plurality of R ^5d are present, the plurality of R ^5d may be the same or different. When a plurality of R ^6e are present, the plurality of R ^5e may be the same or different. When a plurality of R ^5f are present, the plurality of R ^5f may be the same or different.
A combination of two selected from the group consisting of a substituent which the alkyl group represented by ^R5a may have, ^R5d , R5e, and ^R5f , two ^R5d 's, two ^R5e 's, or two ^{R5f 's} may be bonded to each other to form a ring.
At least one of R ^5a , R ^5b and R ^5c is other than a hydrogen atom.
In formula (VI), R ^6a and R ^6b each independently represent an alkyl group which may contain a substituent.
In formula (VII), R ^7a to R ^7c each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a benzene ring group which may have a substituent. A chemical solution containing an organic solvent and used as a developer,
The organic solvent contains only butyl acetate,
Contains at least one first organic compound selected from the group consisting of compounds represented by general formulas (I) to (III),
the first organic compound comprises one or more compounds selected from the group consisting of compound 35, compound 36, and compound 37;
The total content of the first organic compound is 1 to 10,000 ppt by mass relative to the total mass of the chemical solution;
Further, the composition contains at least one second organic compound selected from the group consisting of compounds represented by general formulas (IV) to (VII),
The total content of the second organic compounds is 1 ppt by mass or more and 100,000 ppt by mass or less with respect to the total mass of the chemical solution.
In formula (I), Y represents a benzene ring group which may be substituted with an alkyl group, or a group represented by formula (A).
When Y represents a benzene ring group, s represents 1, L represents a single bond, and R ^1a represents an alkyl group which may contain a substituent. The alkyl group may contain a heteroatom. When the benzene ring group is substituted with an alkyl group, the alkyl group and R ^1a may be bonded to each other to form a ring. When the benzene ring group is substituted with a plurality of alkyl groups, the alkyl groups may be bonded to each other to form a ring.
When Y represents a group represented by formula (A), s represents 3, L represents a methylene group, and each R ^1a independently represents an alkyl group.
In formula (II), R ^2a to R ^2h each independently represent an alkyl group which may contain a substituent.
R ^2b and R ^2e may be bonded to each other to form a ring.
The group formed by combining R ^2b and R ^2e with each other is —O—(—Si(R ²ⁱ ) ₂ —O—) _a —.
a represents an integer of 1 or more.
R ²ⁱ represents an alkyl group which may contain a substituent.
A plurality of R ^2i's may be the same or different.
In formula (III), R ^3a represents -N(R ^3c )R ^3d or -SR ^3e .
R ^3c , R ^3d and R ^3e each represent a hydrogen atom or a substituent.
R ^3b represents -NH- or -S-.
In the general formula (IV), X represents a benzene ring group which may contain a substituent, a cyclohexene ring group which may contain a substituent, or a cyclohexane ring group which contains a cycloalkyloxy group as a substituent. The cyclohexane ring group may further contain another substituent.
In formula (V), R ^5a represents an alkyl group which may contain a substituent, or a hydrogen atom.
R ^5b and R ^5c each independently represent a hydrogen atom, -AL-O-R ^5d , -CO-R ^5e , or -CH(OH)-R ^5f .
AL represents an alkylene group which may contain a substituent.
R ^5d , R ^5e and R ^5f each independently represent a substituent.
When a plurality of R ^5d are present, the plurality of R ^5d may be the same or different. When a plurality of R ^6e are present, the plurality of R ^5e may be the same or different. When a plurality of R ^5f are present, the plurality of R ^5f may be the same or different.
A combination of two selected from the group consisting of a substituent which the alkyl group represented by ^R5a may have, ^R5d , R5e, and ^R5f , two ^R5d 's, two ^R5e 's, or two ^{R5f 's} may be bonded to each other to form a ring.
At least one of R ^5a , R ^5b and R ^5c is other than a hydrogen atom.
In formula (VI), R ^6a and R ^6b each independently represent an alkyl group which may contain a substituent.
In formula (VII), R ^7a to R ^7c each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a benzene ring group which may have a substituent. A chemical liquid containing an organic solvent and used as a pre-wet liquid or a rinse liquid,
The organic solvent contains only 4-methyl-2-pentanol,
Contains at least one first organic compound selected from the group consisting of compounds represented by general formulas (I) to (III),
the first organic compound comprises one or more compounds selected from the group consisting of compound 35, compound 36, and compound 37;
The total content of the first organic compound is 1 to 10,000 ppt by mass relative to the total mass of the chemical solution;
Further, the composition contains at least one second organic compound selected from the group consisting of compounds represented by general formulas (IV) to (VII),
The total content of the second organic compounds is 1 ppt by mass or more and 100,000 ppt by mass or less with respect to the total mass of the chemical solution.
In formula (I), Y represents a benzene ring group which may be substituted with an alkyl group, or a group represented by formula (A).
When Y represents a benzene ring group, s represents 1, L represents a single bond, and R ^1a represents an alkyl group which may contain a substituent. The alkyl group may contain a heteroatom. When the benzene ring group is substituted with an alkyl group, the alkyl group and R ^1a may be bonded to each other to form a ring. When the benzene ring group is substituted with a plurality of alkyl groups, the alkyl groups may be bonded to each other to form a ring.
When Y represents a group represented by formula (A), s represents 3, L represents a methylene group, and each R ^1a independently represents an alkyl group.
In formula (II), R ^2a to R ^2h each independently represent an alkyl group which may contain a substituent.
R ^2b and R ^2e may be bonded to each other to form a ring.
The group formed by combining R ^2b and R ^2e with each other is —O—(—Si(R ²ⁱ ) ₂ —O—) _a —.
a represents an integer of 1 or more.
R ²ⁱ represents an alkyl group which may contain a substituent.
A plurality of R ^2i's may be the same or different.
In formula (III), R ^3a represents -N(R ^3c )R ^3d or -SR ^3e .
R ^3c , R ^3d and R ^3e each represent a hydrogen atom or a substituent.
R ^3b represents -NH- or -S-.
In the general formula (IV), X represents a benzene ring group which may contain a substituent, a cyclohexene ring group which may contain a substituent, or a cyclohexane ring group which contains a cycloalkyloxy group as a substituent. The cyclohexane ring group may further contain another substituent.
In formula (V), R ^5a represents an alkyl group which may contain a substituent, or a hydrogen atom.
R ^5b and R ^5c each independently represent a hydrogen atom, -AL-O-R ^5d , -CO-R ^5e , or -CH(OH)-R ^5f .
AL represents an alkylene group which may contain a substituent.
R ^5d , R ^5e and R ^5f each independently represent a substituent.
When a plurality of R ^5d are present, the plurality of R ^5d may be the same or different. When a plurality of R ^6e are present, the plurality of R ^5e may be the same or different. When a plurality of R ^5f are present, the plurality of R ^5f may be the same or different.
A combination of two selected from the group consisting of a substituent which the alkyl group represented by ^R5a may have, ^R5d , R5e, and ^R5f , two ^R5d 's, two ^R5e 's, or two ^{R5f 's} may be bonded to each other to form a ring.
At least one of R ^5a , R ^5b and R ^5c is other than a hydrogen atom.
In formula (VI), R ^6a and R ^6b each independently represent an alkyl group which may contain a substituent.
In formula (VII), R ^7a to R ^7c each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a benzene ring group which may have a substituent. The chemical solution according to any one of claims 1 to 4, wherein at least one of the first organic compound and the second organic compound has a ClogP value of 5 or more. The chemical solution according to any one of claims 1 to 5, wherein at least one of the second organic compounds is a compound represented by the general formula (VI). The chemical solution according to claim 6, wherein the ratio of the content of the compound represented by the general formula (VI) to the total content of the first organic compound and the second organic compound other than the compound represented by the general formula (VI) is 0.01 to 1. Further, it contains a metal component,
The chemical solution according to any one of claims 1 to 7, wherein the content of the metal component is 0.1 to 500 ppt by mass relative to the total mass of the chemical solution. The chemical solution according to claim 8, wherein the ratio of the total content of the first organic compound to the content of the metal component is 0.01 to 10,000. The drug solution according to any one of claims 1 to 4 further contains a metal component. The chemical solution according to claim 10, wherein the ratio of the total content of the first organic compound and the second organic compound to the content of the metal component is 0.01 to 50,000. The chemical solution according to claim 10 or 11, wherein the metal component contains metal particles and metal ions. The chemical solution according to claim 12, wherein the ratio of the total content of the first organic compound and the second organic compound to the content of the metal particles is 0.01 to 50,000. The chemical solution according to claim 12 or 13, wherein the ratio of the total content of the first organic compound and the second organic compound to the content of the metal ions is 0.03 to 30,000. The chemical solution according to any one of claims 1 to 14, wherein the volume resistivity of the organic solvent is 5,000,000 Ωm or more. A kit containing two or more selected from the group consisting of a pre-wet liquid containing the chemical solution described in claim 1, 2 or 4, a developer containing the chemical solution described in claim 3, and a rinse solution containing the chemical solution described in claim 1, 2 or 4. A container and the drug solution according to any one of claims 1 to 15 contained in the container,
A chemical solution container, the liquid contacting part which comes into contact with the chemical solution in the container being made of electrolytically polished stainless steel or fluorine-based resin. The drug solution container according to claim 17, wherein the void ratio in the container calculated by formula (X) is 5 to 30 volume %.
Formula (X): Porosity = {1 - (volume of the drug solution in the container / container volume of the container)} x 100 A method for manufacturing a semiconductor chip, comprising the steps of: manufacturing a semiconductor chip using the chemical solution according to any one of claims 1 to 15.