TWI857963B - Chemical liquid, chemical liquid accommodation body, kit, method for manufacturing semiconductor chip - Google Patents

Abstract

The present invention provides a chemical solution, a chemical solution container, a reagent box and a method for manufacturing a semiconductor chip with excellent defect suppression. The chemical solution of the present invention contains an organic solvent, and the chemical solution contains at least one first organic compound selected from the group of compounds represented by general formula (I) to general formula (V), and the total content of the first organic compound is 0.01 to 100000 mass ppt relative to the total mass of the chemical solution.

Description

Chemical solution, chemical solution container, reagent box, and method for manufacturing semiconductor chip

The present invention relates to a manufacturing method of a chemical solution, a chemical solution container, a reagent box and a semiconductor chip.

When manufacturing semiconductor devices by a wiring formation step including photolithography, a chemical solution containing water and/or an organic solvent can be used as a pre-wetting solution, a resist solution (resist film formation composition), a developer, a rinse solution, a stripping solution, a chemical mechanical polishing (CMP: Chemical Mechanical Polishing) slurry, and a cleaning solution after CMP, or as a diluent thereof. In recent years, with the advancement of photolithography technology, the miniaturization of patterns has continued to develop. As a method of miniaturizing patterns, a method of shortening the wavelength of the exposure light source can be used. Attempts have been made to use EUV (extreme ultraviolet light) with a shorter wavelength as the exposure light source to replace the previously used ultraviolet light, KrF excimer laser, and ArF excimer laser pattern formation. As the pattern to be formed becomes finer, the above-mentioned chemical solution used in the process is required to have further defect suppression properties.

As a liquid chemical used for pattern formation in the past, Patent Document 1 discloses a "method for producing an organic treatment liquid for pattern formation of a chemically amplified resist film capable of reducing the generation of particles in pattern formation technology (paragraph [0010])". [Prior Technical Document] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2015-084122

As a result of the research conducted by the inventors of the present invention on the organic treatment solution (chemical solution) for pattern formation produced by the above-mentioned manufacturing method, it was found that there is room for improvement in defect suppression. More specifically, when the chemical solution is used as a pre-wetting solution or a rinse solution, there is room for improvement in the suppression of defects such as metal slag defects, particle-shaped organic slag defects, and spot-shaped slag defects. In addition, when the chemical solution is used as a developer for the pattern, there is room for improvement in the suppression of defects such as poor development defects, slag defects, and uniformity defects. The subject of the present invention is to provide a chemical solution with excellent defect suppression as described above. In addition, the subject of the present invention is also to provide a method for manufacturing a chemical solution container, a reagent box, and a semiconductor chip.

In order to solve the above problems, the inventors of the present invention conducted in-depth research and found that the above problems can be solved by the following structure.

(1) A drug solution containing an organic solvent, the drug solution containing at least one first organic compound selected from the group of compounds represented by general formula (I) to general formula (III) described below, The total content of the first organic compound is 0.01 to 100,000 ppt relative to the total mass of the drug solution. (2) The drug solution described in (1), which also contains at least one second organic compound selected from the group of compounds represented by general formula (IV) to general formula (VII) described below. (3) The drug solution described in (2), which contains at least two or more compounds selected from the first organic compound and the second organic compound. (4) The drug solution described in (3), wherein at least one of the two or more compounds has a ClogP value of 5 or more. (5) A drug solution as described in any one of (2) to (4), wherein at least one of the two or more compounds contains a compound represented by the general formula (VI). (6) A drug solution as described in (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) A drug solution as described in any one of (1) to (6), which further contains a metal component, and the content of the metal component is 0.1 to 500 ppt by mass relative to the total mass of the drug solution. (8) A drug solution as described in (7), wherein the ratio of the total content of the first organic compound to the content of the metal component is 0.01 to 10000. (9) A drug solution as described in (2), which further contains a metal component. (10) The chemical solution as described in (9), 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. (11) The chemical solution as described in (9) or (10), wherein the metal component contains metal particles and metal ions. (12) The chemical solution as described in (11), 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. (13) The chemical solution as described in (11) or (12), 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. (14) The drug solution as described in any one of (1) to (13), wherein the organic solvent is selected from 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, ethyl diol, dipropylene glycol, propylene glycol, ethyl carbonate, propylene carbonate, cyclobutane, cycloheptanone, 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, amyl propionate, isoamyl propionate, ethylcyclohexane, trimethylol, decane, 3,7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, 2-octanol, ethyl acetylacetate, dimethyl malonate, methyl pyruvate and dimethyl oxalate. (15) A chemical solution as described in any one of (1) to (14), wherein the volume resistivity of the organic solvent is 5,000,000 Ωm or more. (16) A reagent kit containing two or more selected from the group consisting of: a pre-wetting solution containing a chemical solution described in any one of (1) to (15); a developing solution containing a chemical solution described in any one of (1) to (15); a rinsing solution containing a chemical solution described in any one of (1) to (15); a polishing solution containing a chemical solution described in any one of (1) to (15); and a composition for forming a resist film containing a chemical solution described in any one of (1) to (15). (17) A chemical solution container containing a container and a chemical solution described in any one of (1) to (15) contained in the container, wherein the liquid contact portion in the container that contacts the chemical solution is made of electrolytically polished stainless steel or fluorine-based resin. (18) A chemical solution container as described in (17), wherein the porosity in the container determined by the formula (X) described below is 5 to 30 volume %. (19) A method for manufacturing a semiconductor chip, wherein the semiconductor chip is manufactured using the chemical solution described in any one of (1) to (15). [Effect of the invention]

According to the present invention, a chemical solution with excellent defect suppression can be provided. In addition, according to the present invention, a method for manufacturing a chemical solution container, a reagent box, and a semiconductor chip can also be provided.

The present invention is described in detail below. The description of the constituent elements described below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In addition, in this specification, the numerical range represented by "～" refers to the range that includes the numerical values recorded before and after "～" as the lower limit and upper limit. Furthermore, in the present invention, "ppm" means "parts-per-million: one millionth ( ^10-6 )", "ppb" means "parts-per-billion: one billionth ( ^10-9 )", "ppt" means "parts-per-trillion: one trillionth ( ^10-12 )", and "ppq" means "parts-per-quadrillion: one thousandth ( ^10-15 )". Furthermore, in the marking of the groups (atomic groups) in the present invention, the markings that are not marked with substitution and unsubstituted include not only the groups without substitution but also the groups with substitution within the scope that does not impair the effect of the present invention. For example, the so-called "alkyl" includes not only the alkyl groups without substitution (unsubstituted alkyl groups) but also the alkyl groups with substitution (substituted alkyl groups). This aspect is the same for each compound. Furthermore, the "radiation" in the present invention refers to, for example, far ultraviolet rays, extreme ultraviolet rays (EUV; Extreme ultraviolet), X-rays or electron beams. Furthermore, the "light" in the present invention refers to actinic rays or radiation. The so-called "exposure" in the present invention, unless otherwise specified, includes not only exposure using far ultraviolet rays, X-rays or EUV, but also includes drawing using particle beams such as electron beams or ion beams.

Although the mechanism by which the chemical solution of the present invention solves the above-mentioned problems is not necessarily clear, the inventors speculate on the mechanism as follows. In addition, the following mechanism is a speculation, and even if the effect of the present invention is obtained by a different mechanism, it is also included in the scope of the present invention. There are trace impurities mixed in the chemical solution during storage and transfer through piping, and such impurities are likely to become the cause of various defects. In addition, various defects refer to defects generated when the chemical solution is applied to the manufacturing steps of semiconductor devices. As a more specific example, metal residue defects, particle-shaped organic residue defects, and spot-shaped residue defects occur when the chemical solution is used as a pre-wetting solution or a rinse solution, poor development defects, residue defects, and uniformity defects occur when the chemical solution is used as a developer of a pattern, and defects such as the above occur when the chemical solution is used as a pipe cleaning solution and then the pre-wetting solution, rinse solution, or developer solution is transferred through the cleaned pipe. The chemical solution of the present invention contains a predetermined amount or more of the first organic compound described later, so it shows a saturated solution state, and impurities (especially impurities that are likely to cause defects) are difficult to mix into the chemical solution. On the other hand, by setting the content of the first organic compound to be less than the predetermined amount, it is possible to avoid the first organic compound itself from causing defects. Based on such a mechanism, the inventors of the present invention speculate that in various processes using the chemical solution of the present invention, the occurrence of defects in the final product can be suppressed.

The liquid medicine of the present invention contains an organic solvent and at least one first organic compound selected from the group of compounds represented by general formula (I) to general formula (III) described below, and the total content of the first organic compound is 0.1 to 100,000 ppt relative to the total mass of the liquid medicine. The components contained in the liquid medicine of the present invention are described in detail below.

<Organic solvent> The liquid medicine of the present invention (hereinafter also referred to as "liquid medicine") contains an organic solvent. In this specification, the so-called organic solvent refers to a liquid organic compound containing each component at a content of more than 10,000 mass ppm relative to the total mass of the above-mentioned liquid medicine. That is, in this specification, a liquid organic compound containing more than 10,000 mass ppm relative to the total mass of the above-mentioned liquid medicine is equivalent to an organic solvent. In addition, in this specification, the so-called liquid refers to a liquid at 25°C and atmospheric pressure.

There is no particular restriction on the content of the organic solvent in the liquid medicine, but relative to the total mass of the liquid medicine, 98.00 mass% or more is preferred, more than 99.00 mass% is more preferred, 99.90 mass% or more is further preferred, and more than 99.95 mass% is particularly preferred. The upper limit is less than 100 mass%. One organic solvent may be used alone, or two or more organic solvents may be used. 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 a known organic solvent can be used. Examples of the organic solvent 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), alkyl carbonates, alkyl alkoxyacetates, alkyl pyruvates, dialkyl sulfoxides, cyclic sulfoxides, dialkyl ethers, monohydric alcohols, ethylene glycols, alkyl acetates, and N-alkyl pyrrolidone.

As for the organic solvent, for example, it is selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), propylene carbonate (PC), isopropyl alcohol (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, N-butylene ... -Methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethyl carbonate, cyclobutane, cycloheptanone, 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, amyl propionate, isoamyl propionate, ethylcyclohexane, trimethylol, decane, 3,7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, 2-octanol, ethyl acetylacetate, dimethyl malonate, methyl pyruvate and dimethyl oxalate are preferably used. As examples of using two or more organic solvents, the combined use of PGMEA and PGME and the combined use of PGMEA and PC can be cited. In addition, the type and content of organic solvents in the solution can be measured using a gas chromatography-mass spectrometer.

The volume resistivity of the organic solvent is not particularly limited, but preferably 500,000,000Ωm or more. The upper limit is not particularly limited, but preferably 5,000,000,000Ωm or less. The volume resistivity of the organic solvent can be measured, for example, using a volume resistivity meter SME-8310 or a superinsulation meter SM-8220 manufactured by HIOKI E.E. CORPORATION.

For example, the organic solvent preferably has a distance of 3 to 20 MPa ^0.5 (more preferably 5 to 20 MPa ^0.5 ) relative to the Hansen solubility parameter of eicosene. When two or more organic solvents are used, it is preferred that at least one of them satisfies the above range of Hansen solubility parameters. When two or more organic solvents are used, it is preferred that the weighted average of the Hansen solubility parameters based on the molar ratio of the content of each organic solvent satisfies the above range of Hansen solubility parameters.

For example, from the viewpoint of better defect suppression of the chemical solution, it is also preferred that the organic solvent substantially satisfies the above-mentioned range of Hansen solubility parameters. The organic solvent substantially satisfies the above-mentioned range of Hansen solubility parameters, which means that the content of the organic solvent satisfying the above-mentioned range of Hansen solubility parameters is 99 mass % or more (preferably 99.9 mass % or more) relative to the total mass of the organic solvent.

For example, the organic solvent is preferably a mixed solvent containing both an organic solvent satisfying the above-mentioned Hansen solubility parameter range and an organic solvent not satisfying the above-mentioned Hansen solubility parameter range. In this case, from the viewpoint of obtaining a more excellent defect suppression property of the obtained chemical solution, the mixed solvent preferably contains 20 to 80 mass % (preferably 30 to 70 mass %) of the organic solvent satisfying the above-mentioned Hansen solubility parameter range relative to the total mass of the mixed solvent, and preferably contains 20 to 80 mass % (preferably 30 to 70 mass %) of the organic solvent not satisfying the above-mentioned Hansen solubility parameter range relative to the total mass of the mixed solvent. It is believed that 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 respectively above a certain amount, the affinity of the chemical solution with respect to the metal raw material and the organic raw material can be adjusted within an appropriate range, thereby achieving a more excellent effect of the present invention, compared with a case where the amount of the organic solvent not satisfying the above-mentioned range of Hansen solubility parameters is outside a predetermined range (for example, 1 mass % or more and less than 20 mass % or more than 80 mass % relative to the total mass of the mixed solvent). In this case, the total content of the organic solvent satisfying the above-mentioned Hansen solubility parameter range and the organic solvent not satisfying the above-mentioned Hansen solubility parameter range relative to the total mass of the mixed solution is preferably 99.0 mass % or more. There is no particular upper limit, but it is generally preferably 99.99999 mass % or less. In addition, in the organic solvent that does not satisfy the above range of Hansen solubility parameter, the distance of the Hansen solubility parameter relative 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 less than 50 MPa ^0.5 ).

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

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

[Chemical formula 1]

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

[Chemical formula 2]

In the case where Y represents a benzene ring group, s represents 1, L represents a single bond, and R ^1a represents an alkyl group that may contain a substituent. In addition, the alkyl group may contain a heteroatom (preferably an oxygen atom). In the case where the alkyl group contains an oxygen atom, it is preferably contained in the form of -O- or -CO-. In other words, the above-mentioned alkyl group may contain -O- or -CO-. The alkyl group of R ^1a may be a straight chain or a branched chain, and may also contain a cyclic structure. The carbon number of the alkyl group of R ^1a is preferably 1 to 20, and more preferably 1 to 10. In addition, the carbon number of the alkyl group of R ^1a does not include the number of carbon atoms contained in the 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. It may also contain a substituent). As for the above-mentioned substituent, an aromatic ester group is more preferable. When the benzene ring group represented by Y is substituted by an alkyl group, the above-mentioned alkyl group and R ^1a may be bonded to each other to form a ring. Furthermore, when the benzene ring group represented by Y is substituted by a plurality of alkyl groups, the above-mentioned alkyl groups may be bonded to each other to form a ring.

When Y represents a group represented by the general formula (A), s represents 3, L represents a methylene group, and R ^1a each independently represents an alkyl group. In this case, the carbon number of the alkyl group of R ^1a is preferably 1 to 15, and more preferably 1 to 10. The compounds represented by the general formula (I) are exemplified.

[Chemical formula 3]

In the general formula (II), R ^2a to R ^2h each independently represent an alkyl group which may contain a substituent. R ^2b and R ^2e may bond to each other to form a ring, and the group formed by R ^2b and R ^2e bonding to each other is preferably -O-(-Si(R ²ⁱ ) ₂ -O-) _a -. a represents an integer greater than 1. The upper limit of a is not particularly limited, but in most cases it is less than 10. R ²ⁱ represents an alkyl group which may contain a substituent. The presence of a plurality of R ²ⁱ may be the same or different. The alkyl group represented by R ^2a to R ²ⁱ may be a linear chain or a branched chain, and may also contain a cyclic structure. The carbon number of the above alkyl group is preferably 1 to 10, and more preferably 1 to 5. In addition, the carbon number of the above alkyl group does not include the number of carbon atoms contained in the substituent that the alkyl group may contain. The alkyl groups represented by R ^2a to R ²ⁱ are preferably unsubstituted alkyl groups, and methyl groups are more preferably methyl groups. It is also preferred that one of R ^2g and R ^2h is an alkyl group containing a substituent. It is preferred that the substituent contains one or more oxyalkylene groups (preferably the alkylene moiety has 2 to 4 carbon atoms, and may be linear, branched, or may contain a ring structure). The group containing one or more oxyalkylene groups may contain a hydroxyl group. The compounds represented by the general formula (II) are exemplified.

[Chemical formula 4]

[Chemical formula 5]

In the general formula (III), R ^3a represents -N(R ^3c )R ^3d or -SR ^3e . R ^3c , R ^3d and R ^3e represent a hydrogen atom or a substituent. R ^3b represents -NH- or -S-. As R ^3e , for example, an aromatic thio group can be cited. As the aromatic thio group, a group represented by -S-Ar (Ar: an aromatic cyclic group which may have a substituent) is preferred. The aromatic cyclic group in the above aromatic thio group may contain heteroatoms (sulfur atoms, nitrogen atoms and/or oxygen atoms, etc.), or may not contain heteroatoms, preferably containing heteroatoms. That is, as the aromatic cyclic group, an aromatic heterocyclic group is preferred. The above aromatic cyclic group may be monocyclic or polycyclic, preferably polycyclic. As the aromatic ring group, a benzothiazolyl ring group is preferred. The compounds represented by the general formula (III) are exemplified.

[Chemical formula 6]

The boiling point of the first organic compound is not particularly limited, but from the perspective of not being easily volatile and forming a complex with the metal component, thereby being able to further suppress the generation of defects originating from the metal component, 250°C or above is preferred, and 380°C or above is more preferred. The upper limit is not particularly limited, but in most cases it is 450°C or below. The above boiling point refers to the boiling point under 1 atmosphere of pressure.

The molecular weight of the first organic compound is not particularly limited, but is preferably 300 or more in relation to the above-mentioned boiling point. The upper limit is not particularly limited, but is 1000 or less in most cases.

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

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 from the viewpoint that the first organic compound acts as a hydrophobic compound in the chemical solution and interacts with the metal component, thereby further suppressing the generation of defects originating from the metal component, 3 or more is preferred, and 5 to 10 is more preferred.

The total content of the first organic compound is 0.01 to 100,000 mass ppt relative to the total mass of the liquid medicine. From the perspective of better defect suppression of the liquid medicine (hereinafter referred to as "the perspective of better effect of the present invention"), 80,000 mass ppt or less is preferred, 10,000 mass ppt or less is more preferred, and 2,000 mass ppt or less is further preferred. There is no particular lower limit, but 0.1 mass ppt or more is preferred, and 1 mass ppt or more is more preferred. The first organic compound may be used alone or in combination of two or more. Among them, from the perspective of better effect of the present invention, it is preferred to use two or more.

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

The drug solution may contain other components in addition to the above-mentioned organic solvent and the first organic compound. The other components are described in detail below.

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

[Chemical formula 7]

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 cycloalkoxy group as a substituent. The above-mentioned cyclohexane ring group may also contain other substituents. As other substituents, there can be cited a alkyl group (for example, an unsaturated alkyl group) which may contain at least one selected from the group including a hydroxyl group and a carboxyl group. As a substituent that the benzene ring group may contain, for example, there can be cited an alkyl group, an alkoxy group, and an arylcarbonyl group which may contain a substituent. As a substituent that the cyclohexene ring group may contain, for example, there can be cited an alkenyloxy group and a cyclohexene ring group which may contain a substituent.

Examples of the compound represented by the general formula (IV) include compounds 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 have 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 compounds represented by the general formula (IV) are exemplified.

[Chemical formula 8]

[Chemical formula 9]

In the general formula (V), R ^5a represents an alkyl group which may have a substituent or a hydrogen atom. R ^5b and R ^5c each independently represent a hydrogen atom, -AL-OR ^5d , -CO-R ^5e or -CH(OH)-R ^5f . AL represents an alkylene group which may have a substituent (preferably having 1 to 6 carbon atoms). R ^5d , R ^5e and R ^5f each independently represent a substituent (preferably an alkyl group which may further have a substituent). The alkyl group which may have a substituent represented by R ^5a , R ^5d , R ^5e and R ^5f each independently may be a linear chain, a branched chain, or may have a ring structure. The carbon number of the above alkyl group is preferably 1 to 50, and more preferably 1 to 20. In addition, the carbon number of the above alkyl group does not include the number of carbon atoms contained in the substituent which the alkyl group may have. As the substituent that the above-mentioned alkyl group may contain, for example, a hydroxyl group, an alkyl ester group, and an alkyl vinyl group (preferably, the carbon number of the alkyl part is 3 to 12) can be cited. When there are multiple R ^5d , the multiple R ^5d may be the same or different. When there are multiple R ^5e , the multiple R ^5e may be the same or different. When there are multiple R ^5f , the multiple R ^5f may be the same or different. A combination of two selected from the group including the substituent that the alkyl group represented by R ^5a may contain, R ^5d , R ^5e, and R ^5f , two R ^5d , two R ^5e , or two R ^5f may be bonded to each other to form a ring. The group formed by a combination of two selected from the group consisting of a substituent that the alkyl group represented by R ^5a may have, R ^5d , R ^5e and R ^5f , and two R ^{5d s} , two R ^5e s or two R ^{5f s} bonded to each other 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.

As the compound represented by the general formula (V), there can be mentioned the compound represented by the general formula (V-1).

[Chemical formula 10]

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

The compounds represented by the general formula (V) are exemplified.

[Chemical formula 11]

[Chemical formula 12]

[Chemical formula 13]

In the general 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, and may contain a cyclic structure. The carbon number of the alkyl group is preferably 1 to 20, and more preferably 2 to 10. In addition, the carbon number of the alkyl group does not include the number of carbon atoms contained in the substituent that the alkyl group may contain. As the substituent, for example, an aromatic cyclic group (which may contain a substituent, preferably a phenyl group) is preferred. The compounds represented by the general formula (VI) are exemplified.

[Chemical formula 14]

In the general 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. Among R ^7a to R ^7c , an alkyl group which may have one or more (preferably two or more) substituents or a benzene ring group which may have a substituent is preferred. The above-mentioned alkyl group may be a linear or branched chain, and may also have a ring structure. The carbon number of the above-mentioned alkyl group is preferably 1 to 20, and more preferably 1 to 5. In addition, the carbon number of the above-mentioned alkyl group does not include the number of carbon atoms contained in the substituent that the alkyl group may have. As the above-mentioned substituent, an alkoxy group (preferably having 2 to 6 carbon atoms) or a halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom, etc.) is preferred. As a substituent which the above-mentioned benzene ring group may have, an alkyl group (preferably having 2 to 10 carbon atoms) is preferable. The compounds represented by the general formula (VII) are exemplified.

[Chemical formula 15]

The boiling point of the second organic compound is not particularly limited, but from the perspective of not being easily volatile and forming a complex with the metal component, thereby being able to further suppress the generation of defects originating from the metal component, 250°C or above is preferred, and 380°C or above is more preferred. The upper limit is not particularly limited, but in most cases it is 450°C or below. The above boiling point refers to the boiling point under 1 atmosphere of pressure.

The molecular weight of the second organic compound is not particularly limited, but is preferably 300 or more in relation to the above-mentioned boiling point. The upper limit is not particularly limited, but is 2000 or less in most cases.

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 from the perspective of the second organic compound acting as a hydrophobic compound in the chemical solution and interacting with the metal component to further suppress the generation of defects originating from the metal component, 3 or more is preferred, and 5 to 10 is more preferred.

The total content of the second organic compound is not particularly limited, but from the perspective of a better effect of the present invention, 0.01 to 100,000 mass ppt relative to the total mass of the drug solution is preferred. Among them, from the perspective of a better effect of the present invention, 80,000 mass ppt or less is preferred, 20,000 mass ppt or less is more preferred, 10,000 mass ppt or less is further preferred, and 2,000 mass ppt or less is particularly preferred. There is no particular lower limit, but 0.1 mass ppt or more is preferred, and 1 mass ppt or more is more preferred. The second organic compound can be used alone or in combination. Among them, from the perspective of a better effect of the present invention, it is preferred to use two or more.

In the case where the liquid medicine of the present invention contains the first organic compound and the second organic compound, from the viewpoint of a more excellent effect of the present invention, it is preferable that the liquid medicine of the present invention contains at least two or more compounds of the first organic compound and the second organic compound. For example, a form containing at least one or more of the first organic compound and at least one or more of the second organic compound can be cited. It is preferable that the ClogP of at least one of the above two or more compounds is 5 or more.

Furthermore, at least one of the above two or more compounds is preferably the compound represented by the above general formula (VI). 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 the general formula (VI) to the content of the compound represented by the general formula (VII) is not particularly limited, but is preferably 0.01 to 1.

<Metal component> The liquid medicine may contain a metal component. In the present invention, metal particles and metal ions may be cited as metal components. For example, the content of the metal component means the total content of metal particles and metal ions. The liquid medicine may contain either or both of metal particles and metal ions. It is preferred that the liquid medicine contains both metal particles and metal ions.

Examples of metal elements 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 Zr (zirconium). The metal component may contain one metal element or two or more. Metal particles may be monomers, alloys, or may exist in the form of a combination of metal and organic matter. 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 when the treatment solution is manufactured, stored and/or transferred, or an intentional addition.

From the perspective of better defect suppression of the chemical solution, when the chemical solution contains a metal component, the content is preferably 0.01 to 500 mass ppt, more preferably 0.01 to 250 mass ppt, and even more preferably 0.01 to 100 mass ppt relative to the total mass of the chemical solution. If the content of the metal component is 0.01 mass ppt or more, it is easy to form a complex with the first organic compound (or the second organic compound) mentioned above, so it is easy to remove from the substrate. As a result, the defect suppression can be further improved. In addition, if the content of the metal component is 500 mass ppt or less, it is easy to avoid the increase in defects caused by the metal component.

From the perspective of a better defect suppression performance of the chemical solution, when the chemical solution contains metal ions, the content is preferably 0.01 to 400 mass ppt, more preferably 0.01 to 200 mass ppt, and further preferably 0.01 to 80 mass ppt relative to the total mass of the chemical solution. From the perspective of a better defect suppression performance of the chemical solution, when the chemical solution contains metal particles, the content is preferably 0.01 to 400 mass ppt, more preferably 0.01 to 150 mass ppt, and further preferably 0.01 to 40 mass ppt relative to the total mass of the chemical solution.

In addition, the types and contents of specific metal ions and specific metal particles in the drug solution can be measured by SP-ICP-MS (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry). Here, the so-called SP-ICP-MS method uses the same equipment as the conventional ICP-MS method (Inductively Coupled Plasma Mass Spectrometry), and only the data analysis is different. Data analysis of the SP-ICP-MS method can be performed by commercially available software. In ICP-MS, the content of the metal component to be measured is measured regardless of its existence form. Therefore, the total mass of the metal particles and metal ions to be measured is determined as the content of the metal component.

On the other hand, the content of metal particles can be measured in the SP-ICP-MS method. Therefore, if the content of metal particles is subtracted from the content of metal components in the sample, the content of metal ions in the sample can be calculated. As an apparatus for the SP-ICP-MS method, for example, the Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry: inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200) manufactured by Agilent Technologies can be cited, which can be measured by the method described in the embodiment. As other apparatuses besides the above, in addition to the NexION 350S manufactured by PerkinElmer, the Agilent 8900 manufactured by Agilent Technologies 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 from the viewpoint of a better effect of the present invention, 0.01 to 10000 is preferred, and 0.1 to 5000 is more preferred. 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 from the viewpoint of a better effect of the present invention, 0.01 to 50000 is preferred, and 0.1 to 5000 is more preferred. 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 from the viewpoint of a better effect of the present invention, 0.01 to 50000 is preferred, and 0.05 to 30000 is more preferred. The ratio of the total content of the first organic compound and the second organic compound to the content of the metal ions is not particularly limited, but from the viewpoint of more excellent effects of the present invention, 0.03 to 30,000 is preferred, and 0.05 to 20,000 is more preferred.

<Water> The chemical solution may contain water. There is no particular limitation on the water, and for example, distilled water, ion exchange water, and pure water can be used. Water may be added to the chemical solution, or may be accidentally mixed into the chemical solution during the chemical solution manufacturing step. Examples of situations where water is accidentally mixed into the chemical solution during the chemical solution manufacturing step include situations where water is contained in the raw materials (e.g., organic solvents) used in the chemical solution manufacturing step, and situations where water is mixed (e.g., contaminated) during the chemical solution manufacturing step, but the present invention is not limited to the above.

There is no particular limitation on the water content in the liquid medicine, but it is preferably 0.05 to 2.0 mass % relative to the total mass of the liquid medicine. The water content in the liquid medicine refers to the water content measured by a device using the Karl Fischer moisture measurement method as the measurement principle.

<Resin> The chemical solution may contain a resin. As the resin, a resin P containing a group that generates a polar group by decomposition by the action of an acid (containing a repeating unit of an acid-decomposable group) is more preferred. As the above-mentioned resin, a resin whose solubility in a developer containing an organic solvent as a main component is reduced by the action of an acid, that is, a resin containing a repeating unit represented by the formula (AI) described later is more preferred. The resin containing the repeating unit represented by the formula (AI) described later contains a group that generates an alkali-soluble group by decomposition by the action of an acid. As the polar group, an alkali-soluble group can be cited. Examples of the alkali-soluble group include a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a phenolic hydroxyl group and a sulfone group.

In the acid-decomposable group, a polar group is protected by a group that is released by the action of an acid (acid-released group). Examples of the acid-released 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 independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

_R01 and _R02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

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

(Formula (AI): a repeating unit containing an acid-decomposable group) It is preferred that the resin P contains a repeating unit represented by formula (AI).

[Chemical formula 16]

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. _Ra1 to _Ra3 each independently represent an alkyl group (straight chain or branched chain) or a cycloalkyl group (monocyclic or polycyclic). Two of _Ra1 to _Ra3 may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

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

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

The weight average molecular weight of 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 a polystyrene conversion value based on the GPC (Gel permeation chromatography) method. The dispersity (molecular weight distribution) of resin P is generally 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 liquid medicine, the content of the resin P in the total solid content is preferably 50 to 99.9 mass %, and more preferably 60 to 99.0 mass %. In the liquid medicine, one or more resins P may be used. The solid content refers to the component obtained by removing organic solvents and solvents such as water from the liquid medicine.

In addition, the liquid medicine may also contain known compounds such as acid generators, alkaline compounds, quenchers, hydrophobic resins, and surfactants. The liquid medicine may contain, for example, components contained in photosensitive or radiation-sensitive resin compositions described in Japanese Patent Publication No. 2013-195844, Japanese Patent Publication No. 2016-057645, Japanese Patent Publication No. 2015-207006, International Publication No. 2014/148241, Japanese Patent Publication No. 2016-188385, and Japanese Patent Publication No. 2017-219818.

<Use of the chemical solution> The chemical solution of the present invention is preferably used for the manufacture of semiconductor devices. Among them, it is preferably used to manufacture semiconductor chips. Specifically, in the manufacturing steps of semiconductor elements including lithography steps, etching steps, ion implantation steps and stripping steps, after the completion of each step or before the transfer to the next step, it is used to treat organic matter. Specifically, it is preferably used as a pre-wetting solution, developer, rinse solution and polishing solution. In addition, the chemical solution can also be used as a diluent of the resin contained in the resist film forming composition (in other words, a solvent).

Furthermore, the above-mentioned chemical solution can also be used for purposes other than the manufacture of semiconductor devices, and can also be used as a developer and rinser for polyimide, sensor resist, and lens resist. Furthermore, the above-mentioned chemical solution can also be used as a solvent for medical purposes or cleaning purposes. For example, it can be preferably used for cleaning of piping, containers, and substrates (for example, wafers and glass, etc.). For the above-mentioned cleaning purposes, it is also preferable to use it as a cleaning liquid (pipe cleaning liquid and container cleaning liquid, etc.) for cleaning piping and containers that come into contact with the above-mentioned pre-wetting liquid, etc.

The chemical liquid can be preferably used as a pre-wetting liquid, a developer, a rinse liquid, a polishing liquid, and a resist film forming composition. When used as a pre-wetting liquid, a developer, and a rinse liquid, a more excellent effect is exerted. In addition, when used as a pipe cleaning liquid used in pipes for transferring these liquids, a more excellent effect is exerted.

In addition, it can be used as a reagent kit containing two or more selected from the group consisting of: a pre-wetting solution containing the chemical solution of the present invention; a developer containing the chemical solution of the present invention; a rinse solution containing the chemical solution of the present invention; a polishing solution 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 for producing drug solution> The method for producing the drug solution is not particularly limited, and a known method can be used. From the perspective of obtaining a more excellent effect of the present invention, the method for producing the drug solution preferably includes a filtration step of filtering the purified substance containing an organic solvent using a filter to obtain the drug solution.

The purified product used in the filtration step can be purchased or obtained by reacting the raw materials. The purified product preferably has a small amount of impurities. Examples of commercially available purified products include those called "high-purity grade products".

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

(Filtration step) The method for producing a drug solution of the present invention preferably includes a filtration step of filtering the above-mentioned purified substance using a filter to obtain a drug solution. There is no particular limitation on the method of filtering the purified substance using a filter, but it is preferably a filter unit having a housing and a filter element accommodated in the housing, wherein the purified substance is passed (liquid is passed) under pressure or without pressure.

• Pore diameter of the filter There is no particular restriction on the pore diameter of the filter, and a filter having a pore diameter generally used for filtering a purified substance can be used. From the viewpoint of making it easier to control the amount of particles (metal particles, etc.) contained in the liquid medicine within the desired range, the pore diameter of the filter is preferably 200 nm or less, 20 nm or less is more preferred, 10 nm or less is further preferred, 5 nm or less is particularly preferred, and 3 nm or less is optimal. There is no particular restriction on the lower limit value, but from the viewpoint of productivity, 1 nm or more is generally preferred. In addition, in this specification, the pore diameter and pore diameter distribution of the filter refer to the pore diameter and pore diameter distribution determined by the bubble point of isopropyl alcohol (IPA) or HFE-7200 ("Novec 7200", manufactured by 3M Company, hydrofluoric acid, C ₄ F ₉ OC ₂ H ₅ ).

If the pore diameter of the filter is 5.0 nm or less, it is better from the viewpoint of easier control of the number of particles contained in the liquid medicine. Hereinafter, a filter with a pore diameter of 5 nm or less is also referred to as a "micropore filter". In addition, a micropore filter can be used alone or together with a filter having another pore diameter. Among them, from the viewpoint of better productivity, it is better to use it together with a filter having a larger pore diameter. In this case, if the purified product previously filtered through a filter having a larger pore diameter is passed through the micropore filter, clogging of the micropore filter can be prevented. That is, as for the pore diameter of the filter, when one filter is used, the pore diameter is preferably 5.0 nm or less, and when two or more filters are used, the pore diameter of the filter with the smallest pore diameter is preferably 5.0 nm or less.

There is no particular limitation on the form of using two or more filters having different pore diameters in sequence, but a method of sequentially arranging the filter units described above along the pipeline for conveying the purified material can be cited. In this case, if the flow rate per unit time of the purified material is to be set constant for the pipeline as a whole, a greater pressure may be applied to the filter with a smaller pore diameter than to the filter with a larger pore diameter. In this case, it is preferable to arrange a pressure regulating valve and a damper between the filters to set the pressure applied to the filter with a small pore diameter constant, or to arrange filter units containing the same filters side by side along the pipeline to increase the filtration area. In this way, the number of particles in the liquid can be controlled more stably.

• Filter material There is no particular limitation on the material of the filter, and any known material can be used as the material of the filter. Specifically, in the case of resin, polyamides such as nylon (e.g., 6-nylon and 6,6-nylon); polyolefins such as polyethylene and polypropylene; polystyrene; polyimide; polyamide imide; poly(meth)acrylate; polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride and polyfluorocarbons; polyvinyl alcohol; polyester; cellulose; cellulose acetate, etc. Among them, from the viewpoint of having better solvent resistance and better defect suppression of the obtained solution, at least one selected from the group including nylon (6,6-nylon is preferred), polyolefin (polyethylene is preferred), poly(meth)acrylate and polyfluorocarbon (polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkane (PFA) are preferred). These polymers can be used alone or in combination of two or more. In addition, in addition to resins, diatomaceous earth and glass can also be used. In addition, a polymer (nylon grafted UPE, etc.) obtained by graft-copolymerizing a polyamide (for example, nylon-6 or nylon-6,6) with a polyolefin (UPE, etc. described later) can also be used as a filter material.

Furthermore, the filter may be a filter that has been surface treated. The surface treatment method is not particularly limited, and a known method can be used. Examples of the surface treatment method include chemical modification treatment, plasma treatment, hydrophobic treatment, coating, gas treatment, and sintering.

Plasma treatment makes the surface of the filter hydrophilic, so it is preferred. The water contact angle on the surface of the filter material hydrophilized by plasma treatment is not particularly limited, but the static contact angle measured at 25°C with a contact angle meter is preferably 60° or less, more preferably 50° or less, and even more preferably 30° or less.

As a chemical modification treatment, a method of introducing ion exchange groups into a substrate is preferred. That is, as a filter, a filter in which each of the materials listed above is used as a substrate and ion exchange groups are introduced into the above substrate is preferred. Typically, a filter including a layer of a substrate containing ion exchange groups on the surface of the above substrate is preferred. There is no particular limitation on the substrate to be surface-modified, and from the viewpoint of easier manufacturing, a filter in which ion exchange groups are introduced into the above polymer is preferred.

Regarding the ion exchange group, examples of the cation exchange group include sulfonic acid group, carboxyl group and phosphoric acid group, and examples of the anion exchange group include quaternary ammonium group, etc. The method of introducing the ion exchange group into the polymer is not particularly limited, and a typical method is to react a compound containing an ion exchange group and a polymerizable group with the polymer to perform grafting.

There is no particular limitation on the method of introducing the ion exchange group. Ionizing radiation (α-rays, β-rays, γ-rays, X-rays, electron beams, etc.) is irradiated onto the fiber of the above-mentioned resin to generate active parts (free radicals) in the resin. The irradiated resin is immersed in a solution containing monomers to graft polymerize the monomers onto the substrate. As a result, a polymer is generated that is bonded to the polyolefin fiber as a grafted polymerized side chain. The resin containing the generated polymer as a side chain is contacted with a compound containing an anion exchange group or a cation exchange group to introduce the ion exchange group into the polymer of the grafted polymerized side chain to obtain the final product.

Furthermore, the filter may be a combination of a woven or nonwoven fabric having an ion exchange group formed by radiation graft polymerization and a conventional filter material of glass wool, woven or nonwoven fabric.

If a filter containing an ion exchange group is used, it is easier to control the content of metal components in a drug solution containing metal components (especially particles containing metal atoms) within the desired range. There is no particular restriction on the material of the filter containing an ion exchange group, but materials in which ion exchange groups are introduced into polyfluorocarbons and polyolefins can be cited, and materials in which ion exchange groups are introduced into polyfluorocarbons are more preferred. There is no particular restriction on the pore diameter of the filter containing an ion exchange group, but 1 to 30 nm is preferred, and 5 to 20 nm is more preferred. The filter containing an ion exchange group can be used as the filter with the smallest pore diameter described above, or can be used separately from the filter with the smallest pore diameter. Among them, from the perspective of obtaining a better effect of the present invention, it is preferred to use a filter containing an ion exchange group and a filter without an ion exchange group and having the smallest pore diameter in the filtering step. There is no particular restriction on the material of the filter with the smallest pore diameter described above, but from the perspective of solvent resistance, etc., it is generally preferred to select at least one of the group including polyfluorocarbons and polyolefins, and polyolefins are more preferred.

Therefore, as the filter used in the filtering step, two or more filters made of different materials may be used. For example, two or more filters selected from the group consisting of filters of polyolefins, polyfluorocarbons, polyamides, and materials into which ion exchange groups are introduced may be used.

• Pore structure of the filter There is no particular limitation on the pore structure of the filter, and it can be appropriately selected according to the components in the substance to be purified. In this specification, the pore structure of the filter refers to the pore diameter distribution, the position distribution of the pores in the filter, and the shape of the pores, and can typically be controlled by the manufacturing method of the filter. For example, if a powder of a resin is sintered to form a porous membrane, and if it is formed by methods such as electrospinning, electroblowing, and meltblowing, a fiber membrane can be obtained. The pore structures of these are different.

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

In the case where the purified substance contains negatively charged particles, the polyamide filter functions as a non-sieving membrane to remove such particles. Typical non-sieving membranes include nylon membranes such as nylon-6 membrane and nylon-6,6 membrane, but are not limited to them. In addition, the "non-sieving" retention mechanism used in this specification refers to retention caused by mechanisms such as interference, diffusion, and adsorption that are not related to the pressure reduction or pore size of the filter.

Non-screening retention includes retention mechanisms such as obstruction, diffusion, and adsorption that remove the target particles from the purified material regardless of the pressure reduction of the filter or the pore size of the filter. The adsorption of particles on the filter surface can be mediated by, for example, van der Waals and electrostatic forces between molecules. Particles moving in a non-screening membrane layer with a serpentine passage produce an obstruction effect when they cannot change direction quickly enough to avoid contact with the non-screening membrane. Diffusion-based particle transport is mainly caused by random motion or Brownian motion of small particles, which creates a certain probability of collision between particles and the filter material. When there is no repulsive force between the particles and the filter, the non-screening retention mechanism can become active.

UPE (ultra-high molecular weight polyethylene) filters are typically sieve membranes. Sieve membranes mainly refer to membranes that capture particles through a sieve retention mechanism or membranes that are optimized for capturing particles through a sieve retention mechanism. Typical examples of sieve membranes include polytetrafluoroethylene (PTFE) membranes and UPE membranes, but are not limited to them. In addition, "sieve retention mechanism" refers to the result of retaining particles larger than the pore size of the porous membrane. The sieve retention force can be improved by forming a filter cake (agglomeration of particles to be removed on the surface of the membrane). 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 that can form a fiber membrane. Examples of polymers include polyamides. Examples of polyamides include nylon 6 and nylon 6,6. Poly(ether sulfone) can be used as a polymer to form a fiber membrane. When the fiber membrane is located on the primary side of the porous membrane, it is preferred that the surface energy of the fiber membrane is higher than that of the polymer of the material of the porous membrane located on the secondary side. As such a combination, for example, the case where the material of the fiber membrane is nylon and the porous membrane is polyethylene (UPE) can be used.

The method for producing the fiber film is not particularly limited, and a known method can be used. As the method for producing the fiber film, for example, electrospinning, electroblowing, and melt blowing can be cited as described above.

There is no particular restriction on the pore structure of a porous membrane (for example, a porous membrane including UPE and PTFE), and the shape of the pores may be, for example, lace, string, or node. There is no particular restriction on the size distribution of the pores in the porous membrane and the position distribution in the membrane. The size distribution may be smaller and the distribution position in the membrane may be symmetrical. Alternatively, the size distribution may be larger and the distribution position in the membrane may be asymmetrical (the above membrane is also referred to as an "asymmetric porous membrane"). In an asymmetric porous membrane, the size of the pores varies in the membrane, and typically the pore diameter increases from one surface of the membrane to the other surface of the membrane. At this time, the surface with more pores of larger pore size is called the "open side", and the surface with more pores of smaller pore size is called the "tite side". In addition, as an asymmetric porous membrane, for example, a membrane in which the size of pores is the smallest at a certain position within the thickness of the membrane can be cited (this is also called an "hourglass shape").

If an asymmetric porous membrane is used and the pores on the primary side are set to be larger, in other words, if the primary side is set to be the open side, a pre-filtration effect is produced.

The porous membrane may include thermoplastic polymers such as PESU (polyether sulphate), PFA (perfluoroalkoxyalkane, copolymer of tetrafluoroethylene and perfluoroalkoxyalkane), polyamide and polyolefin, and may also include polytetrafluoroethylene, etc. Among them, ultra-high molecular weight polyethylene is preferred as the material of the porous membrane. Ultra-high molecular weight polyethylene refers to thermoplastic polyethylene with extremely long chains, with a molecular weight of more than one million, typically 2 to 6 million.

As the filter used in the filtering step, two or more filters having different pore structures may be used, and a porous membrane filter and a fiber membrane filter may be used in combination. As a specific example, a method using a nylon fiber membrane filter and a UPE porous membrane filter can be cited.

As described above, filters can be obtained from the market. When such filters are circulated, in most cases, the filters are placed in a packaging bag and sealed, etc., and packaged with packaging materials to avoid contamination. At this time, when the part of the packaging material that can contact the filter (contact part) is polyolefin (polyethylene including high-density polyethylene, etc.), it is easier to cause the problem of impurities adhering to the filter and causing contamination than when the contact part is fluorine-based resin or stainless steel. Therefore, it is better to package the filter with a packaging material in which at least a part of the contact part that contacts the filter is fluorine-based resin or stainless steel.

As the above-mentioned fluorine resin in the contact part, for example, PTFE and PFA can be cited. As the stainless steel in the contact part, the stainless steel described later as a corrosion-resistant material can be cited, among which the contact part is preferably stainless steel (EP-SUS) that has been subjected to electrolytic polishing. Relative to the total area of the contact part, the area of the contact part of the fluorine resin and/or stainless steel is preferably 50-100%, more preferably 90-100%, and further preferably 99-100%. The form of the packaging material is not particularly limited, and it can be a bag form or a capsule form. As for the packaging material, as long as at least a part of the contact portion is fluorine-based resin and/or stainless steel, the entire packaging material may be fluorine-based resin and/or stainless steel, or a composite material with other materials. For example, a composite material having a layered structure in which the contact portion is formed of fluorine-based resin and/or stainless steel, and the portion other than the contact portion is formed of fluorine-based resin and/or stainless steel.

Also, regarding filters, it is best to thoroughly clean them before use. When using an uncleaned filter (or a filter that has not been thoroughly cleaned), impurities contained in the filter can easily enter the drug solution.

As described above, the filtration step of the embodiment of the present invention may be a multi-stage filtration step in which the purified material passes through at least one different filter selected from a group including filter materials, pore diameters, and pore structures. In addition, the purified material may pass through the same filter multiple times, or the purified material may pass through the same type of filter multiple times.

The material of the liquid contact part (referring to the inner wall surface that may contact the purified substance and the chemical solution) of the purification device used in the filtering step is not particularly limited, but it is preferably formed of at least one selected from the group consisting of non-metallic materials (fluorine-based resins, etc.) and electrolytically polished metal materials (stainless steel, etc.) (hereinafter, these are also collectively referred to as "corrosion-resistant materials."). For example, the so-called liquid contact part of the manufacturing tank is formed of a corrosion-resistant material, and the manufacturing tank itself is formed of a corrosion-resistant material, or the inner wall surface of the manufacturing tank is coated with a corrosion-resistant material.

As the above-mentioned non-metallic material, there is no particular limitation, and known materials can be used. As the non-metallic material, for example, at least one selected from the group consisting of polyethylene resin, polypropylene resin, polyethylene-polypropylene resin and fluorine resin (for example, tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene-ethylene copolymer resin, trifluorochloroethylene-ethylene copolymer resin, vinylidene fluoride resin, trifluorochloroethylene copolymer resin and fluoroethylene resin, etc.) can be cited, but it is not limited thereto.

As the above-mentioned metal material, there is no particular restriction, and known materials can be used. As metal materials, for example, metal materials in which the total content of chromium and nickel exceeds 25 mass% relative to the total mass of the metal material can be cited, among which 30 mass% or more is more preferred. There is no particular restriction on the upper limit of the total content of chromium and nickel in the metal material, but it is generally preferred that it is 90 mass% or less. As metal materials, for example, stainless steel and nickel-chromium alloys can be cited.

There is no particular limitation on the stainless steel, and known stainless steel can be used. Among them, alloys containing 8% by mass or more of nickel are preferred, and austenitic stainless steel containing 8% by mass or more of nickel is more preferred. Examples of austenitic stainless steel include SUS (Steel Use Stainless Steel) 304 (Ni content of 8% by mass, Cr content of 18% by mass), SUS304L (Ni content of 9% by mass, Cr content of 18% by mass), SUS316 (Ni content of 10% by mass, Cr content of 16% by mass), and SUS316L (Ni content of 12% by mass, Cr content of 16% by mass).

There is no particular limitation on the nickel-chromium alloy, and a known nickel-chromium alloy can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75% by mass and a chromium content of 1 to 30% by mass is preferred. As nickel-chromium alloys, for example, Hersted alloy (trade name, the same below), Monel alloy (trade name, the same below) and Inconel nickel alloy (trade name, the same below) can be cited. More specifically, Hersted alloy C-276 (Ni content is 63% by mass, Cr content is 16% by mass), Hersted alloy-C (Ni content is 60% by mass, Cr content is 17% by mass) and Hersted alloy C-22 (Ni content is 61% by mass, Cr content is 22% by mass) can be cited. Furthermore, in addition to the above alloys, the nickel-chromium alloy may also contain boron, silicon, tungsten, molybdenum, copper and cobalt as needed.

The method for electrolytically polishing the metal material is not particularly limited, and a known method can be used. For example, the method described in paragraphs [0011] to [0014] of Japanese Patent Application Publication No. 2015-227501 and paragraphs [0036] to [0042] of Japanese Patent Application Publication No. 2008-264929 can be used.

Regarding metal materials, it is estimated that the chromium content in the passivation layer on the surface becomes higher than the chromium content in the parent phase by electrolytic polishing. Therefore, it is estimated that if a purification device is used in which the liquid contact part is formed by the electrolytically polished metal material, it is difficult for the metal component to flow into the purified liquid. In addition, the metal material can also be polished. There is no particular restriction on the polishing method, and a known method can be used. There is no particular restriction on the size of the abrasive grains used in fine polishing, but from the viewpoint that the surface unevenness of the metal material is easy to become smaller, #400 or less is preferred. In addition, it is preferred that polishing be performed before electrolytic polishing.

(Other steps) The method for preparing the drug solution may also have steps other than the filtration step. Examples of steps other than the filtration step include a distillation step, a reaction step, and a deionization step.

(Distillation step) The distillation step is a step of distilling a purified product containing an organic solvent to obtain a distilled purified product. There is no particular limitation on the method of distilling the purified product, and a known method can be used. Typically, a method is exemplified in which a distillation tower is arranged on the primary side of a purification device provided for the filtration step, and the distilled purified product is introduced into a production tank. At this time, there is no particular limitation on the liquid receiving portion of the distillation tower, but it is preferably formed of the corrosion-resistant material described above.

(Reaction step) The reaction step is a step of reacting the raw materials to generate a purified product containing an organic solvent as a reactant. There is no particular limitation on the method for generating the purified product, and a known method can be used. Typically, a method is exemplified in which a reaction tank is arranged on the primary side of a production tank (or a distillation tower) of a purification device for a filtration step, and the reactant is introduced into the production tank (or a distillation tower). At this time, there is no particular limitation on the liquid receiving portion of the production tank, but it is preferably formed of the corrosion-resistant material described above.

(De-electrification step) The de-electrification step is a step of de-electrifying the purified material to reduce the charge potential of the purified material. There is no particular limitation on the de-electrification method, and a known de-electrification method can be used. As a de-electrification method, for example, a method of bringing the purified material into contact with a conductive material can be cited. The contact time for bringing the purified material into contact 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 second. As a conductive material, stainless steel, gold, platinum, diamond, and glassy carbon can be cited. As a method of bringing the object to be purified into contact with the conductive material, for example, there is a method in which a mesh formed of a conductive material and grounded is arranged in a pipe and the object to be purified is passed through the mesh.

Regarding the purification of the purified material, it is preferred that the unsealing of the container attached thereto, the cleaning of the container and the device, the storage of the solution, and the analysis are all performed in a clean room. The clean room is preferably a clean room with a cleanliness level of Class 4 or higher as specified in the international standard ISO14644-1:2015 specified by the International Organization for Standardization. Specifically, it is preferred that any one of ISO Class 1, ISO Class 2, ISO Class 3, and ISO Class 4 be met, and it is more preferred that ISO Class 1 or ISO Class 2 be met, and it is even more preferred that ISO Class 1 be met.

The storage temperature of the drug solution is not particularly limited, but from the viewpoint that impurities contained in a small amount in the drug solution are difficult to dissolve, and as a result, a better effect of the present invention can be obtained, the storage temperature is preferably 4°C or above.

<Drug solution container> The drug solution produced by the above purification method can be contained in a container and stored until it is used. Such a container and the drug solution contained in the container are collectively referred to as a drug solution container. The drug solution is taken out from the stored drug solution container and used.

As a container for storing the above-mentioned chemical solution, for the purpose of semiconductor device manufacturing, it is better to have a high degree of cleanliness inside the container and less elution of impurities. 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 PLASTICS CO., LTD., but the invention is not limited to these.

As a container, it is also preferable to use a multi-layer bottle having a six-layer structure based on six resins or a multi-layer bottle having a seven-layer structure based on six resins for the purpose of preventing impurities from mixing into the drug solution (contamination). As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited.

The liquid contact portion of the container can be made of the corrosion-resistant material described above (preferably electrolytically polished stainless steel or fluorine resin) or glass. From the perspective of obtaining a more excellent effect of the present invention, it is preferred that more than 90% of the area of the liquid contact portion is formed of the above material, and it is even more preferred that the entire liquid contact portion is formed of the above material.

The porosity of the container of the drug solution container is preferably 2 to 80 volume %, more preferably 2 to 50 volume %, and even more preferably 5 to 30 volume %. In addition, the above porosity is calculated according to formula (1). Formula (1): Porosity = {1-(volume of drug solution in container/container volume of container)} × 100 The so-called container volume has the same meaning as the internal volume (capacity) of the container. By setting the porosity within this range, storage stability can be ensured by limiting contamination by impurities, etc. [Example]

The present invention is further described below in detail based on the embodiments. The materials, usage amounts, ratios, processing contents and processing steps shown in the following embodiments can be appropriately changed as long as they do not deviate from the main purpose of the present invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below.

In addition, when preparing the chemical solutions of the embodiments and comparative examples, container handling, chemical solution preparation, filling, storage, and analytical measurements were all performed in a clean room that meets ISO Class 2 or 1.

(Filter) The following filters were used as filters. •Filter A: Activated carbon filter "FCC-S" (fiber) from NIHON FILTER CO., LTD. •"Purasol 200nm": UPE membrane (material) manufactured by Entegris, pore size 200nm •"PTFE 7nm": Polytetrafluoroethylene filter, manufactured by Entegris, pore size 7nm •"UPE 1nm": Ultra-high molecular weight polyethylene filter, manufactured by Pall, pore size 1nm •"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 "5nm": Nylon filter, manufactured by Pall Corporation, pore size is 5nm

<Purified substances> To prepare the chemical solutions of Examples and Comparative Examples, the following organic solvents were used as purified substances. •PGMM: Propylene glycol monomethyl ether •PGME: Propylene glycol monoethyl ether •PGMP: Propylene glycol monopropyl ether •PGMEA: Propylene glycol monomethyl ether acetate (In addition, "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 (In addition, "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 (In addition, "MIBC", "MIBC (A)" to "MIBC (D)" in the table represent five types of MIBC obtained from different companies.) •IPA: Isopropyl alcohol •DMSO: Dimethyl sulfoxide •NMP: N-methylpyrrolidone •DEG: Diethylene glycol •EG: Ethylene glycol •DPG: Dipropylene glycol •PG: Propylene glycol •PC: Propylene carbonate •Sulfolane: Cyclobutane sulfonate •2-Heptanone: 2-Heptanone •nBA: Butyl acetate (In addition, "nBA (A)" to "nBA (D)" in the table represent 4 types of nBA obtained from different companies.) •iAA: Isoamyl acetate •Butyl butyrate •Isobutyl isobutyrate •Isoamyl ether (2.1) •Undecane •Dimethyl malonate (10.3) In addition, the values in parentheses are the distances of the Hansen solubility parameters of isoamyl ether and dimethyl malonate from eicosene (MPa ^0.5 ).

<Container> The following containers were used as containers for the chemical solution. •EP-SUS: Containers with electrolytically polished stainless steel in contact with liquid •PFA: Containers with perfluoroalkoxyalkane coating in contact with liquid

<Purification Step> Select one of the above-mentioned purified substances and perform the distillation purification treatment listed in Table 1. In addition, "Yes-1" in the "Distillation Purification" column in the table indicates that atmospheric distillation using a distillation tower (theoretical number of plates: 15 stages) was carried out, "Yes-2" indicates that reduced pressure distillation using a distillation tower (theoretical number of plates: 25 stages) was carried out, "Yes-3" indicates that reduced pressure distillation using a distillation tower (theoretical number of plates: 30 stages) was carried out twice, "Yes-4" indicates that atmospheric distillation using a distillation tower (theoretical number of plates: 20 stages) was carried out, "Yes-5" indicates that atmospheric distillation using a distillation tower (theoretical number of plates: 10 stages) was carried out, and "Yes-6" indicates that atmospheric distillation using a distillation tower (theoretical number of plates: 8 stages) was carried out. However, "None" in the "Distillation Purification" column in the table means that no distillation treatment was performed. In the case where the "Distillation Purification" column is "None", no distillation purification was performed.

Next, the following circulation filtration treatment was performed: the purified product after distillation was stored in a storage tank, the purified product stored in the storage tank was filtered using filter 1 and filter 2 listed in Table 1, and the purified product after filtering using filter 2 was circulated on the upstream side of filter 1, and filtered again using filter 1 and filter 2. Next, the purified product subjected to the circulation filtration treatment using filter 1 and filter 2 was passed through filter 3 and filter 4 listed in Table 1 in sequence and stored in a storage tank. Next, the following circulation filtration treatment was performed: the purified product stored in the storage tank was filtered using the filter 5 listed in Table 1, and the purified product after being filtered using the filter 5 was circulated on the upstream side of the filter 5 and filtered again using the filter 5. After the circulation filtration treatment, it was stored in a container listed in Table 1 with a predetermined porosity.

In addition, in the above series of purification processes, the liquid contact parts of various devices (such as distillation towers, piping, storage tanks, etc.) that come into contact with the purified material are made of electrolytically polished stainless steel.

The contents of organic components and metal components in the chemical solution were measured by the method shown below.

<Content of organic components> The contents of organic components (first organic compound, second organic compound, etc.) in various chemical solutions were analyzed using a gas chromatograph-mass spectrometer (GC/MS) (manufactured by Agilent, GC: 7890B, MS: 5977B EI/CI MSD).

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

"ClogP" in the table indicates the ClogP value of the organic solvent. "Purity" in the table indicates the content (mass %) of the organic solvent in the obtained solution relative to the total mass of the solution. "Total content 1 (mass ppt)" in the table indicates the total content (mass ppt) of the first organic compound, and "total content 2 (mass ppt)" indicates the total content (mass ppt) of the second organic compound. "Ratio 1" in the table 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 the 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 the metal ion, "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 "porosity" column in the table is the value obtained by formula (X). Formula (X): Porosity = {1-(volume of the drug solution in the container/container volume of the container)}×100

The drug solution obtained as described above contains the compounds shown in the columns "Compound (I)" to "Compound (VII)". Each compound in the "Type" column in the columns "Compound (I)" to "Compound (VII)" in the table indicates the following. In addition, the ClogP values of the compounds described below are as follows. Compound 5: ClogP 6.20 Compound 6: ClogP 8.87 Compound 7: ClogP -2.0～5.0 Compound 8: ClogP -3.0～1.0 Compound 9: ClogP -3.0～1.0 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

[Chemical formula 17]

The * in _L1 in Compound 8 and Compound 9 represents a bonding position.

[Chemical formula 18]

[Chemical formula 19]

[Chemical formula 20]

[Chemical formula 21]

[Chemical formula 22]

[Chemical formula 23]

[Chemical formula 24]

[Chemical formula 25]

[Chemical formula 26]

<Test> [Pre-wetting liquid, rinse liquid] The defect suppression performance of the prepared chemical solution when used as a pre-wetting liquid and a rinse liquid was evaluated by the method shown below. First, the chemical solution was sprayed onto a silicon substrate with a diameter of 300 mm by rotation, and 0.5 cc of each chemical solution was sprayed onto the surface of the substrate while rotating the substrate. Then, the substrate was spin-dried. Next, the number of defects on the substrate after the chemical solution was applied was measured using the wafer inspection device "SP-5" manufactured by KLA-Tencor (this was set as the measured value). Next, using EDAX (energy-dispersive X-ray spectroscopy), the particle-shaped foreign matter in the defects of the wafer was classified into "metal slag defects" with metal as the main component and "particle-shaped organic slag defects" with organic matter as the main component, and the defects were measured separately. Furthermore, the non-particle-shaped spot-shaped defects were counted as "spot-shaped defects". In addition, if any of the evaluations of metal slag defects, particle-shaped organic slag defects, and spot-shaped slag defects is C or above, it contains the defect suppression properties required as a chemical solution.

<Individual evaluation (metal slag defects, particle-shaped organic slag defects, spot-shaped slag defects)> A: The corresponding number of defects is less than 20/wafer. B: The corresponding number of defects exceeds 20/wafer and is less than 50/wafer. C: The corresponding number of defects exceeds 50/wafer and is less than 100/wafer. D: The corresponding number of defects exceeds 100/wafer.

[Developer] The defect suppression property of the prepared chemical solution when used as a developer was evaluated by the method shown below. First, a resist pattern was formed by the operation shown below. ARC29SR (manufactured by NISSAN CHEMICAL CORPORATION), an organic anti-reflection film-forming composition, was coated on a silicon substrate with a diameter of 300 mm and baked at 205°C for 60 seconds to form an anti-reflection film with a film thickness of 78 nm. In order to improve coating properties, a pre-wetting liquid (CyHe of Example 30 was used) was dripped onto the surface of the anti-reflection film side of the silicon wafer on which the anti-reflection film was formed, and spin coating was performed. Next, the (actinic radiation-sensitive resin composition 1) or (actinic radiation-sensitive resin composition 2) described later was applied on the antireflection film after the pre-wetting step, and pre-baked (PB) at 100°C for 60 seconds to form a resist film with a film thickness of 150 nm. In addition, (actinic radiation-sensitive resin composition 1) was used in Examples 49 to 59 and Comparative Examples 3 to 4, and (actinic radiation-sensitive resin composition 2) was used in Examples 60 to 70.

(Photosensitive or radiation-sensitive resin composition 1) Acid-decomposable resin (resin represented by the following formula (weight average molecular weight (Mw): 7500): the value recorded in each repeating unit represents mole %): 100 parts by mass

[Chemical formula 27]

The following photoacid generator: 8 parts by weight

[Chemical formula 28]

The quencher shown below: 5 parts by mass (the mass ratio is 0.1:0.3:0.3:0.2 from the left). In the following quenchers, the weight average molecular weight (Mw) of the polymer type quencher is 5000. In addition, the numerical values recorded in each repeating unit represent the molar ratio.

[Chemical formula 29]

The hydrophobic resin shown below: 4 parts by mass (the mass ratio is set to 0.5:0.5 from the left). In addition, the weight average molecular weight (Mw) of the hydrophobic resin on the left side of the following hydrophobic resin is 7000, and the weight average molecular weight (Mw) of the hydrophobic resin on the right side is 8000. In addition, in each hydrophobic resin, the value recorded in each repeating unit represents the molar ratio.

[Chemical formula 30]

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

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

[Chemical formula 31]

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

The following photoacid generator: 15 parts by weight

[Chemical formula 32]

The quencher shown below: 7 parts by mass (the mass ratio is set to 1:1 from the left.)

[Chemical formula 33]

The hydrophobic resin shown below: 20 parts by mass (the mass ratio is set to 3:7 from the top). In addition, the weight average molecular weight (Mw) of the hydrophobic resin in the upper section of the following hydrophobic resin is 10,000, and the weight average molecular weight (Mw) of the hydrophobic resin in the lower section is 7,000. In addition, in the hydrophobic resin shown in the lower section, the numerical value recorded in each repeating unit represents the molar ratio.

[Chemical formula 34]

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

For the wafer with the resist film formed on it, the pattern was exposed at 25mJ/ ^cm2 using an ArF excimer laser scanner (Numerical Aperture: 0.75). Then, it was heated at 120°C for 60 seconds. Then, liquid development was performed for 30 seconds using each developer (chemical solution). Then, the wafer was rotated at 4000rpm 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 steps, an L/S pattern with a line/space ratio of 1:1 was obtained (average pattern width: 45nm). For each pattern, the developability and defect suppression were evaluated.

<Defect suppression> The pattern of the formed wafer was observed using a pattern defect device (manufactured by Hitachi High-Technologies Corporation., multi-purpose SEM (Scanning Electron Microscope) "Inspago" RS6000 series), and the number of defects below was measured. • Development defect: a defect in which the space is not formed to the bottom of the pattern • Residue defect: a defect in which foreign matter exists on the pattern • Uniformity defect: a defect in which the pattern width is more than ±1nm relative to the specified value In addition, if any of the evaluations of development defect, residue defect, and uniformity defect is C or above, it contains the defect suppression required as a chemical solution.

<Individual evaluation (development defects, residue defects, uniformity defects)> AA: The corresponding number of defects is 3 or less per wafer. A: The corresponding number of defects is more than 3 per wafer and less than 5 per wafer. B: The corresponding number of defects is more than 5 per wafer and less than 10 per wafer. C: The corresponding number of defects is more than 10 per wafer and less than 30 per wafer. D: The corresponding number of defects is more than 30 per wafer.

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

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10]

[Table 11]

[Table 12]

[Table 13]

[Table 14]

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

According to the results shown in the table, it is confirmed that the defect suppression property is excellent when the chemical solution of the present invention is applied to the manufacture of semiconductor devices. Among them, according to the comparison of Example 23, Example 24, Example 32, Example 33, Example 41, Example 42 and other examples, when the content of the metal component is 0.1 to 500 mass ppt relative to the total mass of the chemical solution, the effect is more excellent. Moreover, according to the comparison of Example 26, Example 35, Example 44 and other examples, when the total content 1 (the total content of the first organic compound) is 10000 mass ppt or less (preferably 2000 mass ppt or less), the effect is more excellent. Furthermore, according to the comparison between Example 23, Example 25 and other examples, when the ratio 1 (the ratio of the total content of the first organic compound to the content of the metal component) is 0.01 to 10000, the effect is more excellent.

《EUV exposure》 (Photosensitive or radiation-sensitive resin composition (resist composition 1)) First, the components were mixed in the following composition to obtain a resist composition 1. • Resin (A-1): 0.77 g • Photoacid generator (B-1): 0.03 g • Alkaline compound (E-3): 0.03 g • PGMEA (commercially available, high purity grade): 67.5 g • Ethyl lactate (commercially available, high purity grade): 75 g

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

[Chemical formula 35]

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

[Chemical formula 36]

•Alkaline compound (E-3) As the alkaline compound (E-3), the following compound was used.

[Chemical formula 37]

(Formation and evaluation of patterns) First, AL412 (manufactured by Brewer Science) was applied on a silicon wafer with a diameter of 300 mm and baked at 200°C for 60 seconds to form a 20nm thick resist underlayer film. A pre-wetting liquid (cyclohexanone/manufactured by FFUS) was applied on it, and a resist composition was applied from it, and baked at 100°C for 60 seconds (PB: Prebake) to form a 30nm thick resist film.

The resist film was exposed through a reflective mask using an EUV exposure machine (manufactured by ASML; NXE3350, NA0.33, dipole 90°, outer sigma 0.87, inner sigma 0.35). Then, it was heated at 85°C (PEB: Post Exposure Bake) for 60 seconds. Next, a developer (butyl acetate/FETW) was sprayed for 30 seconds and developed, and a rinse solution was sprayed on the silicon wafer for 20 seconds by a spin coating method and rinsed. Then, the silicon wafer was rotated at 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. As the above-mentioned rinse liquid, the liquid used in the above-mentioned Examples 1 to 48 and Examples 71 to 75 were used respectively. In addition, the evaluation results of the above-mentioned metal slag defects, particulate organic slag defects, and spot-like slag defects can obtain the desired effect with the same tendency as Table 1 [1] <7>.

without

without

without.

Claims (19)

A drug solution comprising an organic solvent, wherein the drug solution comprises at least one first organic compound selected from the group consisting of compounds represented by general formula (I) to general formula (III), wherein the total content of the first organic compound is 0.01 mass ppt to 100000 mass ppt relative to the total mass of the drug solution,

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

In the case where Y represents a benzene ring group, s represents 1, L represents a single bond, R ^1a represents an alkyl group which may have a substituent, and the alkyl group may contain a heteroatom. In the case where the benzene ring group is substituted by an alkyl group, the alkyl group and R ^1a may be bonded to each other to form a ring. In the case where a plurality of alkyl groups are substituted by the benzene ring group, the alkyl groups may be bonded to each other to form a ring. In the case where Y represents a group represented by the general formula (A), s represents 3, L represents a methylene group, and R ^1a each independently represents an alkyl group. In the general formula (II), R ^2a to R ^2h each independently represents an alkyl group which may have a substituent, R ^2b and R ^2e may be bonded to each other to form a ring. The group formed by R ^2b and R ^2e bonding to each other is -O-(-Si(R ²ⁱ ) ₂ -O-) _a -, a represents an integer greater than 1, R ²ⁱ represents an alkyl group which may have a substituent, and a plurality of R ²ⁱ may be the same or different. In the general formula (III), R ^3a represents -N(R ^3c )R ^3d or -SR ^3e , R ^3c , R ^3d and R ^3e represent a hydrogen atom or a substituent, and R ^3b represents -NH- or -S-. The drug solution as described in item 1 of the patent application further contains at least one second organic compound selected from the group consisting of compounds represented by general formula (IV) to general formula (VII),

In the general formula (IV), X represents a benzene ring group which may have a substituent, a cyclohexene ring group which may have a substituent, or a cyclohexane ring group which has a cycloalkoxy group as a substituent, and the above cyclohexane ring group may also have other substituents. In the general formula (V), R ^5a represents an alkyl group which may have a substituent or a hydrogen atom, R ^5b and R ^5c each independently represent a hydrogen atom, -AL-OR ^5d , -CO-R ^5e or -CH(OH)-R ^5f , AL represents an alkylene group which may have a substituent, R ^5d , R ^5e and R ^5f each independently represent a substituent, and when there are multiple R ^{5d s} , the multiple R ^{5d s} may be the same or different, and when there are multiple R ^{5e s} , the multiple R 5c s may be the same or different. ^{R 5e} may be the same or different. When there are plural R ^5f , the plural R ^5f may be the same or different and are selected from the group consisting of a substituent which the alkyl group represented by R ^5a may have, a combination of two of R ^5d , R ^5e and R ^5f , two R ^5d , two R ^5e or two R ^5f may bond 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 the general formula (VI), R ^6a and R ^6b each independently represent an alkyl group which may have a substituent. In the general formula (VII), R ^7a to R ^7c each independently represent a hydrogen atom, an alkyl group which may have a substituent or a phenyl ring group which may have a substituent. The liquid medicine as described in item 2 of the patent application contains at least two or more compounds of the first organic compound and the second organic compound. The drug solution as described in item 3 of the patent application scope, wherein the ClogP value of at least one of the two or more compounds is greater than 5. The drug solution as described in item 3 or 4 of the patent application scope, wherein at least one of the two or more compounds contains the compound represented by the general formula (VI). As described in item 5 of the patent application scope, 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 0.01~1. The liquid medicine described in any one of Items 1 to 4 of the patent application scope also contains a metal component, and the content of the metal component is 0.1 mass ppt~500 mass ppt relative to the total mass of the liquid medicine. As described in item 7 of the patent application scope, the ratio of the total content of the first organic compound to the content of the metal component is 0.01~10000. The liquid medicine described in Item 2 of the patent application also contains metal components. As described in item 9 of the patent application scope, the ratio of the total content of the first organic compound and the second organic compound to the content of the metal component is 0.01~50000. The liquid medicine described in item 9 or 10 of the patent application, wherein the metal component contains metal particles and metal ions. As described in item 11 of the patent application scope, the ratio of the total content of the first organic compound and the second organic compound to the content of the metal particles is 0.01~50000. As described in item 11 of the patent application scope, the ratio of the total content of the first organic compound and the second organic compound to the content of the metal ion is 0.03~30000. The liquid medicine as described in any one of items 1 to 4 of the patent application, wherein the organic solvent is selected from 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, propylene glycol, ethyl carbonate, propylene carbonate, cyclobutane, cycloheptanone, 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, amyl propionate, isoamyl propionate, ethylcyclohexane, trimethylol, decane, 3,7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, 2-octanol, ethyl acetylacetate, dimethyl malonate, methyl pyruvate and dimethyl oxalate. For a liquid medicine as described in any one of items 1 to 4 of the patent application scope, the volume resistivity of the organic solvent is 5,000,000 Ωm or more. A reagent kit, which contains two or more selected from the group consisting of: a pre-wetting solution containing a chemical solution described in any one of items 1 to 15 of the patent application; a developer containing a chemical solution described in any one of items 1 to 15 of the patent application; a rinse solution containing a chemical solution described in any one of items 1 to 15 of the patent application; a polishing solution containing a chemical solution described in any one of items 1 to 15 of the patent application; and a resist film forming composition containing a chemical solution described in any one of items 1 to 15 of the patent application. A liquid medicine container, comprising a container and a liquid medicine described in any one of items 1 to 15 of the patent application scope contained in the container, wherein the liquid contacting portion in the container that contacts the liquid medicine is made of electrolytically polished stainless steel or fluorine-based resin. As described in item 17 of the patent application, the porosity of the container obtained by formula (X) is 5-30 volume %, formula (X): porosity = {1-(volume of the drug solution in the container/container volume of the container)}×100. A method for manufacturing a semiconductor chip, wherein the semiconductor chip is manufactured using a chemical solution described in any one of items 1 to 15 of the patent application scope.