TWI838502B - Process liquid, and method for forming pattern - Google Patents

Abstract

The subject of the present invention is to provide a resist film patterning treatment liquid and a pattern forming method capable of simultaneously suppressing the occurrence of pattern collapse and film loss in the exposed portion. The treatment liquid of the present invention is used for at least one of developing and washing a resist film obtained by photosensitive radiation or a radiation-sensitive composition, and the resist film patterning treatment liquid contains an organic solvent, and contains a first organic solvent that meets specified conditions and a second organic solvent that meets specified conditions.

Description

Treatment solution, pattern forming method

The present invention relates to a processing liquid for forming a resist film pattern and a pattern forming method. More specifically, the present invention relates to a processing liquid and a pattern forming method used in semiconductor manufacturing steps such as IC (Integrated Circuit), manufacturing of circuit substrates such as liquid crystal and thermal head, and other lithography steps of inductive etching processing.

In the past, micro-processing was performed by lithography using resist compositions in the manufacturing process of semiconductor devices such as IC (Integrated Circuit) and LSI (Large Scale Integrated Circuit). In recent years, with the high integration of integrated circuits, there is a demand for the formation of ultra-fine patterns in sub-micron and quarter-micron areas. As a result, the exposure wavelength has also shown a tendency to become shorter, such as from g-rays to i-rays, and further to KrF excimer lasers. In addition to excimer lasers, the development of lithography using electron beams, X-rays, or EUV (Extreme Ultra Violet) is also being promoted. In this type of lithography, after a film is formed by a resist composition (also called an actinic ray or radiation-sensitive composition, or a chemically amplified resist composition), the obtained film is developed by a developer or washed with a rinser. For example, Patent Document 1 discloses that an organic processing liquid containing a mixture of a first organic solvent selected from a ketone solvent and an ester solvent and a second organic solvent is used as a developer.

[Patent Document 1] Japanese Patent Application Publication No. 2012-181523

In recent years, with the high integration of integrated circuits, there is a demand to form fine patterns using resist compositions (photosensitive radiation or radiation-sensitive compositions). In the formation of such fine patterns, the distance between patterns becomes narrower as the miniaturization occurs, which generates a strong capillary force and easily causes the problem of "pattern collapse" when forming L/S (line and space) patterns. In addition, as the miniaturization occurs, the film thickness of the pattern also tends to become thinner, so it is more significantly required than before to solve the performance degradation of the pattern caused by "film loss in the exposed part" during the development and washing processes. In other words, a developer and a washing solution that can solve the generation of pattern collapse and film loss in the exposed part at the same time are required.

The present invention is made in view of the above problems, and its subject is to provide a resist film patterning treatment solution and a pattern forming method that can simultaneously suppress the occurrence of pattern collapse and film damage in the exposed part.

After conducting in-depth research on the above-mentioned subject, the inventors found that the above-mentioned subject can be solved by the following structure, and completed the present invention.

[1] A treatment liquid for resist film patterning, which is used for at least one of developing and cleaning a resist film obtained by photosensitive radiation or a radiation-sensitive composition, and contains an organic solvent, and contains: a first organic solvent that satisfies the following condition A and a second organic solvent that satisfies the following condition B. Condition A: A hydrocarbon solvent, an ether solvent, or an ester solvent having an SP value of 18.7 MPa ^1/2 or less and a ΔP represented by the following formula (1) of 15.0 or less, or a ketone solvent having an SP value of 18.7 MPa ^1/2 or less and a ΔP represented by the following formula (1) of 20.0 or less. Condition B: An alcohol solvent having an SP value of 19.0 MPa ^1/2 or more and a ClogP of 1.6 or more, or an ester solvent having an SP value of 19.0 MPa ^1/2 or more, a ΔH represented by the following formula (2) of 20.0 or more, and containing two or more carbonyl groups. Formula (1): ΔP = δp/(δd+δp+δh)×100 Formula (2): ΔH = δh/(δd+δp+δh)×100 In formulas (1) and (2), δd represents the dispersion term of the Hansen solubility parameter. δp represents the polar term of the Hansen solubility parameter. δh represents the hydrogen bond term of the Hansen solubility parameter. [2] The treatment solution as described in [1], wherein in the above condition B, the above alcohol solvent includes an acyclic alcohol solvent, and the above ester solvent includes an acyclic ester solvent. [3] The treatment solution as described in [2], wherein the above acyclic ester solvent includes one or more selected from ethyl acetylacetate, dimethyl malonate, pyruvate and diethyl oxalate. [4] The treatment solution as described in [2], wherein the above acyclic alcohol solvent includes one or more selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2,6-dimethyl-4-heptanol, 2-ethyl-1-hexanol, 1-heptanol, 2-octanol, 1-octanol and 1-hexanol. [5] The treatment solution as described in [2], wherein the acyclic alcohol solvent comprises at least one of 2,6-dimethyl-4-heptanol and 3-octanol. [6] The treatment solution as described in [2], wherein the acyclic alcohol solvent has a triple bond in the molecule. [7] The treatment solution as described in [6], wherein the acyclic alcohol solvent comprises at least one selected from 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol. [8] The treatment solution as described in any one of [1] to [7], wherein in the first organic solvent, the hydrocarbon solvent comprises a hydrocarbon solvent having 7 or more carbon atoms. [9] The treatment liquid as described in any one of [1] to [8], wherein in the first organic solvent, the hydrocarbon solvent comprises at least one selected from ethylcyclohexane, trimethylol, 1,5-cyclooctadiene, undecane and decane. [10] The treatment liquid as described in any one of [1] to [9], wherein in the first organic solvent, the ether solvent comprises at least one selected from amyl ethers, butyl ethers and diisopropyl ether. [11] The treatment liquid as described in any one of [1] to [10], wherein in the first organic solvent, the ether solvent comprises at least one selected from diisoamyl ether and diisobutyl ether. [12] The treatment liquid as described in any one of [1] to [11], wherein the ester solvent in the first organic solvent comprises at least one selected from isobutyl isobutyrate, butyl butyrate, ethyl 2-methyl-pentanoate, hexyl acetate, isobutyl butyrate and butyl isobutyrate. [13] The treatment liquid as described in any one of [1] to [12], wherein the ketone solvent in the first organic solvent comprises at least one selected from diisobutyl ketone and 3-octanone. [14] The treatment liquid as described in any one of [1] to [13], wherein the treatment liquid is a rinse liquid. [15] The treatment liquid as described in any one of [1] to [14], wherein the photosensitive radiation or radiation-sensitive composition comprises a resin having a repeating unit represented by the general formula (1) described below. [16] A pattern forming method, comprising: a resist film forming step, using photosensitive radiation or a radiation-sensitive composition to form a resist film; an exposure step, exposing the resist film; and a treatment step, treating the exposed resist film using a treatment solution described in any one of [1] to [14]. [17] A pattern forming method, comprising: a resist film forming step, forming a resist film using photosensitive radiation or a radiation-sensitive composition; an exposure step, exposing the resist film; and a treatment step, treating the exposed resist film, wherein the treatment step comprises: a developing step, developing with a developer; and a rinsing step, rinsing with a rinse, wherein the rinse is any one of the treatment solutions described in [1] to [14]. [18] The pattern forming method as described in [17], wherein the developer contains an ester solvent. [19] The pattern forming method as described in [18], wherein the ester solvent comprises one or more selected from butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, amyl propionate, hexyl propionate, heptyl propionate, butyl butyrate, butyl isobutyrate and isobutyl isobutyrate. [20] The pattern forming method as described in any one of [16] to [19], wherein the photosensitive radiation or radiation-sensitive composition comprises a resin having a repeating unit represented by the general formula (1) described below. [Effects of the Invention]

According to the present invention, a resist film patterning treatment solution and a pattern forming method can be provided, which can simultaneously suppress the occurrence of pattern collapse and film damage in the exposed portion.

The present invention is described in detail below. The description of the constituent elements described below is sometimes completed based on the representative implementation of the present invention, but the present invention is not limited to such implementation. In the marking of the group (atomic group) in this specification, as long as it does not violate the purpose of the present invention, the marking without substitution and unsubstituted also includes the group without substitution and the group with substitution. For example, "alkyl" includes not only the alkyl group without substitution (unsubstituted alkyl group) but also the alkyl group with substitution (substituted alkyl group). In addition, "organic group" in this specification refers to a group containing at least one carbon atom. "Actinic rays" or "radiation" in this specification refers to, for example, the bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam). "Light" in this specification refers to actinic rays or radiation. "Exposure" in this specification, unless otherwise specified, includes not only exposure using the bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, but also drawing using particle beams such as electron beams and ion beams. In this specification, "～" is used to mean that the numerical values recorded before and after it are included as lower limits and upper limits. Unless otherwise specified, the bonding direction of the divalent groups marked in this specification is not limited. For example, when Y in the compound represented by the general formula "X-Y-Z" is -COO-, Y can be -CO-O- or -O-CO-. In addition, the above compound can be "X-CO-O-Z" or "X-O-CO-Z".

In this specification, (meth)acrylate refers to acrylate and methyl acrylate, and (meth)acrylic acid ((meth)acryl) refers to acrylic acid (acryl) and methacrylic acid (methacryl). In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersity (also called molecular weight distribution) (Mw/Mn) of the resin are defined as polystyrene-equivalent values obtained by GPC measurement using a GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran (THF); flow rate (sample injection amount): 10 μL; column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION; column temperature: 40°C; flow rate: 1.0 mL/min; detector: differential refractive index detector).

The acid dissociation constant pKa in this manual means the acid dissociation constant pKa in aqueous solution, and is defined, for example, in Chemical Handbook (II) (Revised 4th edition, 1993, edited by the Chemical Society of Japan, Maruzen. Inc.). The lower the value of the acid dissociation constant pKa, the greater the acid strength. Specifically, the acid dissociation constant pKa in aqueous solution can be measured by measuring the acid dissociation constant at 25°C using an infinitely diluted aqueous solution. Alternatively, the following software package 1 can be used to calculate and obtain the value based on the database of Hammett's substituent constant and known literature values. All pKa values described in this manual represent values obtained by calculation using the software package. Package 1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).

1Å is 1× ^10-10 m.

In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[Processing liquid] The processing liquid of the present invention is a processing liquid for resist film patterning containing an organic solvent and used for at least one of developing and washing a resist film obtained by photosensitive radiation or a radiation-sensitive composition (hereinafter, also referred to as a "resist composition"). The processing liquid of the present invention contains a first organic solvent that satisfies the condition A described below and a second organic solvent that satisfies the condition B described below.

EUV light (wavelength 13.5nm) has a shorter wavelength than ArF excimer laser light (wavelength 193nm), and therefore has the following characteristics: when the sensitivity is the same during exposure of the resist film, the number of incident photons is smaller. As a result, in lithography using EUV light, the influence of "photon shot noise" where the number of photons is scattered in probability is greater, and it becomes one of the factors that produce highly polar residue components such as highly polar polymer residue. This highly polar residue component becomes the cause of defects (especially bridge defects) on the pattern. This time, the inventors have found that proton polar solvents and ester solvents with high hydrogen bond interaction energy are very effective in reducing highly polar residue components, but if these solvents are used alone, they have low volatility and will become a factor that deteriorates the resolution in dense patterns (in other words, causes pattern collapse in dense patterns). Based on the above research results, the inventors have further studied and the results confirmed that the defects (especially bridge defects) and pattern collapse of the formed pattern can be suppressed by the treatment solution containing the above-mentioned first organic solvent and the above-mentioned second organic solvent, and the film loss of the exposed part can also be suppressed. In addition, the above-mentioned first organic solvent mainly plays a role in reducing highly polar residue components.

Furthermore, it was confirmed that when a solvent with higher volatility is used as the second organic solvent in the above-mentioned processing liquid to improve the volatility of the entire processing liquid, the drying time after the treatment (for example, rinsing treatment) by the above-mentioned processing liquid can be reduced, and the effect of suppressing pattern collapse in dense patterns becomes more significant.

Hereinafter, the first organic solvent and the second organic solvent will be described respectively.

[First organic solvent] The treatment liquid of the present invention contains a first organic solvent that satisfies the following condition A. Condition A: A hydrocarbon solvent, ether solvent or ester solvent having an SP value of 18.7 MPa ^1/2 or less and a ΔP represented by the following formula (1) of 15.0 or less (hereinafter, also referred to as "solvent A-1"). Alternatively, a ketone solvent having an SP value of 18.7 MPa ^1/2 or less and a ΔP represented by the following formula (1) of 20.0 or less (hereinafter, also referred to as "solvent A-2"). Formula (1): ΔP =δp/(δd+δp+δh)×100 In formula (1), δd represents the dispersion term of the Hansen solubility parameter. δp represents the polar term of the Hansen solubility parameter. δh represents the hydrogen bond term of the Hansen solubility parameter. From the perspective of further suppressing pattern collapse, the smaller ΔP is and the larger ΔD (expressed as δd/(δd+δp+δh)) is, the better.

<SP value> In this manual, the "SP value" is calculated according to the following formula using the Fedors method described in "PROPERTIES OF POLYMERS, 2nd edition, published in 1976". In addition, unless otherwise specified, the unit of the SP value is MPa ^1/2 . SP value (Fedors method) = [(sum of cohesive energy of each substituent) / (sum of volume of each substituent)] ^0.5 In addition to the values described in "PROPERTIES OF POLYMERS, 2nd edition, published in 1976", the parameters (cohesive energy and volume) of each substituent can be described using literature values, etc. In addition, the smaller the SP value, the less polar the solvent becomes. That is, the smaller the SP value of the solvent, the lower the affinity with the resist film, so it is possible to suppress excessive penetration into the resist film, that is, it is possible to suppress swelling.

<Hansen solubility parameter> Hansen solubility parameter (δ) is defined as three-dimensional parameters (δd, δp, δh) and is expressed by the following formula (3). In addition, the details related to Hansen solubility parameters are described in "PROPERTIES OF POLYMERS" (author: DWVAN KREVELEN, publisher: ELSEVIER SCIENTIFIC PUBLISHING COMPANY, published in 1989, 5th edition). Formula (3) δ ² = (δd) ² + (δp) ² + (δh) ² δd represents the dispersion term (also called the London dispersion force term). δp represents the polar term (also called the molecular polarization term). δh represents the hydrogen bond term. δd, δp, and δh can be calculated using the program HSPiP (Hansen Solubility Parameters in Practice) developed by the team of Dr. Hansen, who proposed the Hansen solubility parameters. In addition, the δd, δp, and δh in this manual are the values calculated using HSPiP 5th Edition 5.2.06.

In this specification, δd, δp and δh in the above formula (1) and the formula (2) described later have the same meanings as δd, δp and δh in the above formula (3), respectively.

<Solvent A-1> Solvent A-1 is a hydrocarbon solvent, ether solvent or ester solvent having an SP value of 18.7 MPa ^1/2 or less and ΔP represented by the above formula (1) of 15.0 or less. The processing liquid of the present invention contains solvent A-1, so that pattern collapse of the formed pattern is suppressed and film loss in the exposed part is suppressed. In addition, the lower limit of the SP value is, for example, 14.0 MPa ^1/2 or more, and the lower limit of ΔP is, for example, 0.0 or more. Solvent A-1 is described below.

(Hydrocarbon solvents having an SP value of 18.7 MPa ^1/2 or less and a ΔP of 15.0 or less) As hydrocarbon solvents having an SP value of 18.7 MPa ^1/2 or less and a ΔP of 15.0 or less, as long as the SP value and ΔP satisfy the specified values, any of aliphatic hydrocarbon solvents and unsaturated aliphatic hydrocarbon solvents may be used. The number of double bonds or triple bonds possessed by the unsaturated hydrocarbon solvent is not particularly limited, and may be located at any position in the hydrocarbon chain. Furthermore, when the unsaturated hydrocarbon solvent has a double bond, a cis-isomer and a trans-isomer may exist as a mixture. In addition, the carbon number of the hydrocarbon solvent is preferably 7 or more from the viewpoint of further improving the suppression of pattern collapse of the formed pattern and/or the suppression of film loss in the exposed portion. The upper limit is not particularly limited, and for example, 16 or less, 14 or less is preferred, and 12 or less is more preferred.

Specific examples of hydrocarbon solvents having an SP value of 18.7 MPa ^1/2 or less and a ΔP of 15.0 or less are shown below. In addition, the units of each numerical value are omitted. Examples include ethylcyclohexane (SP value: 16.4, ΔP: 0.0), trimethylolbenzene (SP value: 18.6, ΔP: 3.1), 1,5-cyclooctadiene (SP value: 14.3, ΔP: 12.9), undecane (SP value: 15.9, ΔP: 0.0), and decane (SP value: 15.8, ΔP: 0.0).

As the above-mentioned hydrocarbon solvent, those selected from ethylcyclohexane (SP value: 16.4, ΔP: 0.0), trimethylolbenzene (SP value: 18.6, ΔP: 3.1), 1,5-cyclooctadiene (SP value: 14.3, ΔP: 12.9), undecane (SP value: 15.9, ΔP: 0.0) and decane (SP value: 15.8, ΔP: 0.0) are preferred, those selected from ethylcyclohexane, trimethylolbenzene, 1,5-cyclooctadiene and undecane are more preferred, and those selected from ethylcyclohexane, trimethylolbenzene and 1,5-cyclooctadiene are further preferred.

(Ether solvents with an SP value of 18.7 MPa ^1/2 or less and a ΔP of 15.0 or less) As ether solvents with an SP value of 18.7 MPa ^1/2 or less and a ΔP of 15.0 or less, there are no particular restrictions as long as the SP value and ΔP satisfy the prescribed values. In addition, an ether solvent means a solvent having at least one ether bond in the molecule. For example, when a solvent has an ether bond and a functional group other than an ether bond, it is regarded as an ether solvent of Solvent A-1 as long as the SP value and ΔP satisfy the prescribed values.

As the ether solvent, an alcohol solvent having a SP value of 18.7 MPa ^1/2 or less, a ΔP of 13.5 or less, and a ΔD of 73.0 or more is preferred. The upper limit of ΔD is, for example, 100.0 or less.

The following are specific examples of ether solvents having an SP value of 18.7 MPa ^1/2 or less and a ΔP of 15.0 or less. In addition, the units of the numerical values are omitted. Examples include amyl ethers such as diamyl ether (also known as di-n-amyl ether, SP value: 16.2, ΔP: 14.3) and diisoamyl ether (SP value: 15.6, ΔP: 12.1); butyl ethers such as dibutyl ether (also known as di-n-butyl ether, SP value: 15.9, ΔP: 14.2) and diisobutyl ether (SP value: 15.2, ΔP: 12.2); and diisopropyl ether (SP value: 14.6, ΔP: 14.9).

Among them, diisoamyl ether (SP value: 15.6, ΔP: 12.1) or diisobutyl ether (SP value: 15.2, ΔP: 12.2) is preferred as the ether-based solvent, and diisoamyl ether is more preferred.

(Ester-based solvents having an SP value of 18.7 MPa ^1/2 or less and a ΔP of 15.0 or less) As ester-based solvents having an SP value of 18.7 MPa ^1/2 or less and a ΔP of 15.0 or less, there are no particular restrictions as long as the SP value and ΔP satisfy the prescribed values. In addition, an ester-based solvent refers to a solvent having one or more ester bonds in the molecule. For example, when a solvent has an ester bond and a functional group other than an ester bond, as long as the SP value and ΔP satisfy the prescribed values, it is regarded as an ester-based solvent of Solvent A-1.

Specific examples of ester solvents having an SP value of 17.8 MPa ^1/2 or less and a ΔP of 15.0 or less are shown below. In addition, the units of the numerical values are omitted. Examples include isobutyl isobutyrate (SP value: 17.1, ΔP: 14.2), butyl butyrate (SP value: 17.8, ΔP: 12.0), ethyl 2-methylvalerate (SP value: 17.4, ΔP: 14.8), hexyl acetate (SP value: 17.8, ΔP: 11.8), isobutyl butyrate (SP value: 16.8, ΔP: 14.3), butyl isobutyrate (SP value: 16.8, ΔP: 14.5), isobutyl isovalerate (SP value: 17.7, ΔP: 13.1), isoamyl isobutyrate (SP value: 17.7, ΔP: 13.5) and isoamyl acetate (SP value: 17.4, ΔP: 12.2).

The ester solvent preferably has 8 or more carbon atoms, more preferably 8 or 9 carbon atoms, and is selected from isobutyl isobutyrate (SP value: 17.1, ΔP: 14.2), butyl butyrate (SP value: 17.8, ΔP: 12.0), ethyl 2-methyl-pentanoate (SP value: 17.4, ΔP: 14.8), hexyl acetate (SP value: 17.8, ΔP: 11.8), isobutyl butyrate (SP value: 16.8, ΔP: 14.3), butyl isobutyrate (SP value: 16 .8, ΔP: 14.5), isobutyl isovalerate (SP value: 17.7, ΔP: 13.1), isoamyl isobutyrate (SP value: 17.7, ΔP: 13.5) and isoamyl acetate (SP value: 17.4, ΔP: 12.2) are further preferred, and isobutyl isobutyrate, butyl butyrate, ethyl 2-methyl-valerate, hexyl acetate, isobutyl butyrate and butyl isobutyrate are particularly preferred. From the viewpoint of having a carbon number of 8 or more and a smaller ΔP, butyl butyrate is the best.

From the viewpoint of further suppressing the pattern collapse of the formed pattern, the ester solvent preferably has a ΔD of 64.5 MPa ^1/2 or more.

<Solvent A-2> Solvent A-2 is a ketone-based solvent having an SP value of 17.8 MPa ^1/2 or less and a ΔP represented by the following formula (1) of 20.0 or less. The processing liquid of the present invention contains solvent A-2, so that pattern collapse of the formed pattern is suppressed and film loss in the exposed portion is suppressed. In addition, the lower limit of the SP value is, for example, 17.0 MPa ^1/2 or more, and the lower limit of ΔP is, for example, 0.0 or more. Solvent A-2 is described below.

(A ketone-based solvent having an SP value of 17.8 MPa ^1/2 or less and a ΔP of 20.0 or less represented by the following formula (1)) As a ketone-based solvent having an SP value of 17.8 MPa ^1/2 or less and a ΔP of 20.0 or less represented by the following formula (1), there is no particular limitation as long as the SP value and ΔP satisfy the prescribed values. In addition, a ketone-based solvent means a solvent having at least one ketone group in the molecule. For example, when a solvent has a ketone group and a functional group other than a ketone group, it is regarded as a ketone-based solvent of Solvent A-2 as long as the SP value and ΔP satisfy the prescribed values.

The following are specific examples of ketone solvents having an SP value of 17.8 MPa ^1/2 or less and a ΔP of 20.0 or less. In addition, the units of each numerical value are omitted. Examples include diisobutyl ketone (SP value: 17.4, ΔP: 18.6) and 3-octanone (SP value: 17.5, ΔP: 18.1).

As the solvent A, from the viewpoint of being able to further suppress pattern collapse and/or the viewpoint of being able to further suppress film loss in the exposed portion, the solvent A-1 selected from hydrocarbon solvents and ether solvents is preferred.

The treatment solution of the present invention may use the first organic solvent alone or in combination of two or more.

[Second organic solvent] The treatment solution of the present invention contains a second organic solvent that satisfies the following condition B. Condition B: An alcohol-based solvent having an SP value of 19.0 MPa ^1/2 or more and a ClogP of 1.6 or more (hereinafter, also referred to as "solvent B-1"). Alternatively, an ester-based solvent having an SP value of 19.0 MPa1 ^1/2 or more and a ΔH represented by the following formula (2) of 20.0 or more, and containing two or more carbonyl groups (hereinafter, also referred to as "solvent B-2"). Formula (2): ΔH = δh/(δd+δp+δh)×100

<SP value, Hansen solubility parameter> The definition of SP value and Hansen solubility parameter (δd, δp, δh) are as described above.

<ClogP> In this manual, the ClogP of a solvent is a value obtained by calculating the common logarithm logP of the partition coefficient P for 1-octanol and water. The method and software used in the calculation of the ClogP value can be used in the public knowledge. Unless otherwise specified, this manual uses the ClogP program incorporated in ChemDraw ver 16.0.1.4 (77) of PerkinElmer, Inc. In addition, a high ClogP indicates a high affinity for hydrophobic molecules (1-octanol as an index) compared to water molecules.

<Solvent B-1> Solvent B-1 is an alcoholic solvent having an SP value of 19.0 MPa ^1/2 or more and a ClogP of 1.6 or more. The treatment solution of the present invention has excellent suppression of defects (especially bridge defects) in the pattern formed by containing solvent B-1. In addition, the upper limit of the SP value is, for example, 21.0 MPa ^1/2 or less, and the upper limit of the ClogP is, for example, 4.0 or less. As solvent B-1, an alcoholic solvent having an SP value of 19.0 MPa ^1/2 or more and a ClogP greater than 1.6 is preferred.

As an alcoholic solvent having an SP value of 19.0 MPa ^1/2 or more and a ClogP of 1.6 or more, there is no particular limitation as long as the SP value and ClogP satisfy the prescribed values. In addition, an alcoholic solvent means a solvent having at least one alcohol group in the molecule. For example, when a solvent has an alcohol group and a functional group other than the alcohol group, as long as the SP value and ΔP satisfy the prescribed values, it is regarded as an alcoholic solvent of solvent B-1.

Specific examples of alcoholic solvents having an SP value of 19.0 MPa ^1/2 or more and a ClogP of 1.6 or more are shown below. In addition, the units of each numerical value are omitted. Examples include 3,7-dimethyl-3-octanol (SP value: 19.7, ClogP: 3.5), 3,5,5-trimethyl-1-hexanol (SP value: 20.5, ClogP: 3.1), 3-ethyl-3-pentanol (SP value: 20.8, ClogP: 2.1), 2,6-dimethyl-4-heptanol (SP value: 19.9, ClogP: 3.0), 2-ethyl-1-hexanol (SP value: 20.7, ClogP: 2.8), 1-heptanol (SP value: 21.4, ClogP: 2.4), 2-octanol (SP value: 20.7, ClogP : 2.7), 1-octanol (SP value: 21.0, ClogP: 4.0), 1-hexanol (SP value: 21.9, ClogP: 2.4), 3-octanol (SP value: 20.7.0, ClogP: 2.7), 1-octyne-3-ol (SP value: 26.9, ClogP: 2.1), 3,5-dimethyl-1-hexyne-3-ol (SP value: 26.1, ClogP: 1.8), 1-heptyne-3-ol (SP value: 20.5, ClogP: 1.6) and 7-octyne-1-ol (SP value: 20.3, ClogP: 1.6), etc.

As the alcohol solvent, a non-cyclic alcohol solvent is preferred from the viewpoint of suppressing the dissolution of the resist in the exposure portion. As the non-cyclic alcohol solvent, for example, it is preferred to include one or more of the solvents belonging to the first group, one or more of the solvents belonging to the second group, or one or more of the solvents belonging to the third group as shown below. ･Group 1: 3,7-dimethyl-3-octanol (SP value: 19.7, ClogP: 3.5), 3,5,5-trimethyl-1-hexanol (SP value: 20.5, ClogP: 3.1), 3-ethyl-3-pentanol (SP value: 20.8, ClogP: 2.1), 2,6-dimethyl-4-heptanol (SP value: 19.9, ClogP: 3.0), 2-ethyl-1-hexanol (SP value: 20.7, ClogP: 2.8), 1-heptanol (SP value: 21.4, ClogP: 2.4), 2-octanol (SP value: 20.7, ClogP: 2.7), 1-octanol (SP value: 21.0, ClogP: 4.0) and 1-hexanol (SP value: 21.9, ClogP: 2.4). As the solvent of the first group, from the viewpoint of being able to further suppress pattern collapse and/or the viewpoint of being able to further suppress film damage in the exposed portion, 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2,6-dimethyl-4-heptanol, 2-ethyl-1-hexanol and 2-octanol are preferred, and 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2,6-dimethyl-4-heptanol and 2-octanol are further preferred.

･Group 2: 2,6-dimethyl-4-heptanol (SP value: 19.9, ClogP: 3.0) and 3-octanol (SP value: 20.7.0, ClogP: 2.7). As a solvent of Group 2, 3-octanol is preferred from the viewpoint of further suppressing pattern collapse and/or further suppressing film loss in the exposed part.

･Group 3: Non-cyclic alcohol solvents having a triple bond in the molecule. The non-cyclic alcohol solvents having a triple bond in the molecule are not particularly limited. The number of triple bonds possessed by the alcohol solvent is not particularly limited. As the alcohol solvent, a linear or branched aliphatic alcohol solvent is preferred. As for the carbon number of the alcohol solvent, 7 or more is preferred from the viewpoint of further improving the suppression of pattern collapse of the formed pattern and/or the suppression of film loss in the exposed part. The upper limit is not particularly limited, and for example, 14 or less, 12 or less is preferred, and 10 or less is more preferred. As the solvent of the third group, from the viewpoint of being able to further suppress pattern collapse and/or being able to further suppress film damage in the exposed portion, 1-octyne-3-ol (SP value: 26.9, ClogP: 2.1), 3,5-dimethyl-1-hexyne-3-ol (SP value: 26.1, ClogP: 1.8), 1-heptyne-3-ol (SP value: 20.5, ClogP: 1.6) and 7-octyne-1-ol (SP value: 20.3, ClogP: 1.6) are preferred.

<Solvent B-2> Solvent B-2 is an ester solvent having an SP value of 19.0 MPa1 ^1/2 or more and a ΔH of 20.0 or more, and containing two or more carbonyl groups. The processing liquid of the present invention has excellent suppression of defects (especially bridge defects) in the pattern formed by containing solvent B-2. In addition, the upper limit of the SP value is, for example, 21.0 MPa ^1/2 or less, and the upper limit of the ΔH is, for example, 30.0 or less.

As an ester solvent having an SP value of 19.0 MPa1 ^1/2 or more and a ΔH of 20.0 or more, and containing two or more carbonyl groups, there is no particular limitation as long as the SP value and ΔH meet the specified values and contain two or more carbonyl groups. In addition, an ester solvent means a solvent having at least one ester bond in the molecule. For example, when a solvent has an ester bond and a functional group other than an ester bond, as long as the SP value and ΔH meet the specified values and contain two or more carbonyl groups, it is regarded as an ester solvent of solvent B-2. In addition, the above-mentioned carbonyl group may also be a carbonyl group contained in an ester bond.

The following are specific examples of ester solvents having an SP value of 19.0 MPa1 ^1/2 or more and a ΔH of 20.0 or more, and containing two or more carbonyl groups. In addition, the units of each numerical value are omitted. Examples include acetylacetic acid esters such as ethyl acetylate (SP value: 20.7, ΔH: 25.9), dimethyl malonate (SP value: 20.6, ΔH: 29.1), methyl pyruvate (SP value: 21.6, ΔH: 24.5), and ethyl pyruvate (SP value: 21.1, ΔH: 23.3), and diethyl oxalate (SP value: 21.75, ΔH: 26.7).

As the above-mentioned ester solvent, from the viewpoint of both suppressing the dissolution of the resist in the exposed part and removing the residue, a non-cyclic ester solvent is preferred, and one selected from ethyl acetylacetate (SP value: 20.7, ΔH: 25.9), dimethyl malonate (SP value: 20.6, ΔH: 29.1), methyl pyruvate (SP value: 21.6, ΔH: 24.5), ethyl pyruvate (SP value: 21.1, ΔH: 23.3) and diethyl oxalate (SP value: 21.75, ΔH: 26.7) is preferred. From the viewpoint of being able to further suppress the pattern collapse and/or being able to further suppress the film damage in the exposed part, ethyl acetylacetate, methyl pyruvate or ethyl pyruvate is more preferred.

As the solvent B, the solvent B-1 is preferable from the viewpoint of being able to further suppress pattern collapse and/or being able to further suppress film loss in the exposed portion.

The treatment solution of the present invention may use a single second organic solvent or may use two or more second organic solvents in combination.

[Contents of the first organic solvent and the second organic solvent] As the content of the first organic solvent, it is preferably 10% by mass or more relative to the total mass of the treatment liquid, 20% by mass or more is more preferred, 40% by mass or more is further preferred, and 60% by mass or more is particularly preferred. In addition, the upper limit is not particularly limited, for example, 95% by mass or less is preferred, 90% by mass or less is more preferred, and 80% by mass or less is further preferred. As the content of the second organic solvent, it is preferably 10% by mass or more relative to the total mass of the treatment liquid, 20% by mass or more is more preferred, 40% by mass or more is further preferred, and 60% by mass or more is particularly preferred. Moreover, the upper limit value is not particularly limited, for example, 95% by mass or less is preferred, 90% by mass or less is more preferred, 80% by mass or less is further preferred, and 60% by mass or less is particularly preferred. The content of the first organic solvent relative to the total content of the first organic solvent and the second organic solvent is preferably 10% by mass or more, 20% by mass or more is more preferred, 30% by mass or more is further preferred, 40% by mass or more is further preferred, 50% by mass or more is particularly preferred, and 60% by mass or more is the best. Moreover, as the upper limit value, 90% by mass or less is preferred, 80% by mass or less is more preferred, 60% by mass or less is further preferred, and 50% by mass or less is particularly preferred.

In the treatment liquid of the present invention, the total content of the first organic solvent and the second organic solvent relative to the total mass of the treatment liquid is preferably 95.0 mass % or more, more preferably 98.0 mass % or more, further preferably 99.0 mass % or more, particularly preferably 99.5 mass % or more, and most preferably 99.9 mass % or more. In addition, the upper limit is, for example, 100 mass %.

[Preferred forms of the first organic solvent and the second organic solvent] The specific preferred forms of the first organic solvent and the second organic solvent are described below. In addition, as the best combination of the first organic solvent and the second solvent, the first organic solvent is a solvent A-1 selected from hydrocarbon solvents and ether solvents, and the second organic solvent is an alcohol solvent of solvent B-1.

<When the treatment liquid contains an ether solvent as the first organic solvent, and contains an alcohol solvent as the second organic solvent> When the treatment liquid contains an ether solvent as the first organic solvent, and contains an alcohol solvent as the second organic solvent, it is preferred that the first organic solvent and the second organic solvent satisfy at least one of the following A1 to A8. A1: The second organic solvent includes one or more selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2,6-dimethyl-4-heptanol, 2-ethyl-1-hexanol and 2-octanol, or includes one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or includes a non-cyclic alcohol solvent having a triple bond in the molecule (preferably one or more selected from 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol). In A1, the second organic solvent preferably contains one or more selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2,6-dimethyl-4-heptanol and 2-octanol, or contains one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or contains a non-cyclic alcohol solvent having a triple bond in the molecule (preferably one or more selected from 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol). A2: The ΔP of the first organic solvent is less than 13.5 and the ΔD is greater than 73.0 (preferably diisoamyl ether). A3: The ΔP of the first organic solvent is 13.5 or less and the ΔD is 73.0 or more, the second organic solvent includes 3,7-dimethyl-3-octanol, and the content of the first organic solvent is 20-80% by mass relative to the total content of the first organic solvent and the second organic solvent. A4: The ΔP of the first organic solvent is 13.5 or less and the ΔD is 73.0 or more, the second organic solvent includes any one of 3,5,5-trimethyl-1-hexanol and 3-ethyl-3-pentanol, and the content of the first organic solvent is 40-80% by mass relative to the total content of the first organic solvent and the second organic solvent. A5: The second organic solvent contains 2,6-dimethyl-4-heptanol, and the content of the first organic solvent is 80% by mass or less relative to the total content of the first organic solvent and the second organic solvent. A6: The second organic solvent is 2-ethyl-1-hexanol, and the content of the first organic solvent is 40% by mass or more relative to the total content of the first organic solvent and the second organic solvent. A7: The second organic solvent is 2-ethyl-1-hexanol, and the content of the first organic solvent is less than 40% by mass relative to the total content of the first organic solvent and the second organic solvent. A8: The first organic solvent has a ΔP of 13.5 or less and a ΔD of 73.0 or more, the second organic solvent includes 2-octanol, and the content of the first organic solvent is 20 to 80 mass % relative to the total content of the first organic solvent and the second organic solvent.

<When the treatment liquid contains an ether solvent as the first organic solvent, solvent A-1, and an ester solvent as the second organic solvent> When the treatment liquid contains an ether solvent as the first organic solvent, solvent A-1, and an ester solvent as the second organic solvent, solvent B-2, it is preferred that the first organic solvent and the second organic solvent satisfy the following B1 and/or the following B2. B1: The content of the first organic solvent is 50% by mass or more (preferably 80% by mass or more) relative to the total content of the first organic solvent and the second organic solvent. B2: The second organic solvent is ethyl acetylacetate, and the content of the first organic solvent is 80 mass % or more relative to the total content of the first organic solvent and the second organic solvent.

<When the treatment liquid contains a hydrocarbon solvent of solvent A-1 as the first organic solvent and an alcohol solvent of solvent B-1 as the second organic solvent> When the treatment liquid contains a hydrocarbon solvent of solvent A-1 as the first organic solvent and an alcohol solvent of solvent B-1 as the second organic solvent, it is preferred that the first organic solvent and the second organic solvent satisfy at least one of the following C1 to C6. C1: The second organic solvent includes one or more selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2,6-dimethyl-4-heptanol and 2-octanol (preferably 2,6-dimethyl-4-heptanol) or one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or an acyclic alcohol solvent having a triple bond in the molecule (preferably one or more selected from 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol). In C1, the second organic solvent preferably includes one or more selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2,6-dimethyl-4-heptanol and 2-octanol, or includes one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or includes a non-cyclic alcohol solvent having a triple bond in the molecule (preferably one or more selected from 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol). C2: The second organic solvent contains 3,7-dimethyl-3-octanol, and the content of the first organic solvent is 40-80 mass % (preferably 60-80 mass %) relative to the total content of the first organic solvent and the second organic solvent. C3: The second organic solvent contains one or more selected from 3,5,5-trimethyl-1-hexanol and 3-ethyl-3-pentanol, and the content of the first organic solvent is 20-80 mass % (preferably 40-80 mass %) relative to the total content of the first organic solvent and the second organic solvent. C4: The second organic solvent contains 2-octanol, and the content of the first organic solvent is 20-80 mass % relative to the total content of the first organic solvent and the second organic solvent.

C5: The second organic solvent contains 2-ethyl-1-hexanol, and the content of the first organic solvent is less than 40% by mass relative to the total content of the first organic solvent and the second organic solvent. C6: The first organic solvent contains 1,5-cyclooctadiene, the second organic solvent contains 2-ethyl-1-hexanol, and the content of the first organic solvent is less than 40% by mass relative to the total content of the first organic solvent and the second organic solvent.

<When the treatment liquid contains a hydrocarbon solvent of solvent A-1 as the first organic solvent and an ester solvent of solvent B-2 as the second organic solvent> When the treatment liquid contains a hydrocarbon solvent of solvent A-1 as the first organic solvent and an ester solvent of solvent B-2 as the second organic solvent, it is preferred that the first organic solvent and the second organic solvent satisfy the following D1 and/or the following D2. D1: The content of the first organic solvent is 50% by mass or more (preferably 80% by mass or more) relative to the total content of the first organic solvent and the second organic solvent. D2: The second organic solvent is ethyl acetylacetate, and the content of the first organic solvent is 80 mass % or more relative to the total content of the first organic solvent and the second organic solvent.

<Case in which the treatment liquid contains an ester solvent as the first organic solvent and contains an alcohol solvent as the second organic solvent> When the treatment liquid contains an ester solvent as the first organic solvent and contains an alcohol solvent as the second organic solvent, it is preferred that the first organic solvent and the second organic solvent satisfy at least one of the following E1 to E5. E1: The second organic solvent comprises one or more selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2-octanol and 2,6-dimethyl-4-heptanol (preferably 2-octanol or 2,6-dimethyl-4-heptanol), or comprises one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or comprises an acyclic alcohol solvent having a triple bond in the molecule (preferably one or more selected from 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol). In E1, the second organic solvent preferably comprises 2-octanol or any one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or a non-cyclic alcohol solvent having a triple bond in the molecule (preferably one or more selected from 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol). As E1, the second organic solvent comprises one or more of 2,6-dimethyl-4-heptanol and 3-octanol or a non-cyclic alcohol solvent having a triple bond in the molecule (preferably one or more selected from 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol), and the content of the first organic solvent is preferably 60 mass % or more relative to the total content of the first organic solvent and the second organic solvent. E2: The first organic solvent includes an organic solvent having an SP value of 18.7 MPa ^1/2 or less, ΔP of 15.0 or less, and ΔD of 64.5 or more, the second organic solvent includes 3,7-dimethyl-3-octanol, and the content of the first organic solvent is 40 to 80% by mass relative to the total content of the first organic solvent and the second organic solvent. E3: The first organic solvent includes an organic solvent having an SP value of 18.7 MPa ^1/2 or less, ΔP of 15.0 or less, and ΔD of 64.5 or more, the second organic solvent includes one or more selected from 3,5,5-trimethyl-1-hexanol and 3-ethyl-3-pentanol, and the content of the first organic solvent is 20 to 80% by mass relative to the total content of the first organic solvent and the second organic solvent. E4: The first organic solvent includes an organic solvent having an SP value of 18.7 MPa ^1/2 or less, ΔP of 15.0 or less, and ΔD of 64.5 or more, and the second organic solvent includes at least one selected from 2-octanol or 2,6-dimethyl-4-heptanol. E5: The first organic solvent includes an organic solvent having an SP value of 18.7 MPa ^1/2 or less, ΔP of 15.0 or less, and ΔD of 64.5 or more, and the second organic solvent is 2-ethyl-1-hexanol, and the content of the first organic solvent is less than 40 mass % relative to the total content of the first organic solvent and the second organic solvent.

<When the treatment liquid contains a ketone-based solvent as the first organic solvent, and contains an alcohol-based solvent as the second organic solvent> When the treatment liquid contains a ketone-based solvent as the first organic solvent, and contains an alcohol-based solvent as the second organic solvent, it is preferred that the first organic solvent and the second organic solvent satisfy at least one of the following F1 to F4. F1: The second organic solvent includes one or more selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2-octanol and 2,6-dimethyl-4-heptanol, or includes one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or includes a non-cyclic alcohol solvent having a triple bond in the molecule (preferably one or more selected from 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol). In F1, the second organic solvent preferably contains 2-octanol or one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or contains a non-cyclic alcohol solvent having a triple bond in the molecule (preferably one or more selected from 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol). F2: The second organic solvent contains 3,7-dimethyl-3-octanol, and the content of the first organic solvent is 40 to 80 mass % relative to the total content of the first organic solvent and the second organic solvent. F3: The second organic solvent includes at least one selected from 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol and 2-octanol, and the content of the first organic solvent is 20-80% by mass relative to the total content of the first organic solvent and the second organic solvent. F4: The second organic solvent is 2-ethyl-1-hexanol, and the content of the first organic solvent is less than 40% by mass relative to the total content of the first organic solvent and the second organic solvent.

[Other components] The treatment solution of the present invention only needs to contain at least one of the first organic solvent and the second organic solvent, and may also contain other components other than the first organic solvent and the second organic solvent.

<Ionic liquid> Furthermore, the processing liquid of the present invention may also contain the following ionic liquids. When the processing liquid contains an ionic liquid, it is regarded that the ionic liquid is not contained in the first organic solvent and the second organic solvent. The ionic liquid may include, for example, an ionic liquid having, as cations, aromatic ions such as pyridinium ions or imidazolium ions, or aliphatic amine ions such as trimethylhexylammonium ions, and, as anions, inorganic ions such as _NO3- ^, _CH3CO2- ^, _BF6- ^, or _PF6- ^, or fluorine _- containing organic anions such as ( _CF3SO2 ⁾ _2N- ^, _CF3CO2- , _{or CF3SO2-} ; preferably _, ^a quaternary _ammonium salt ionic liquid.

Examples of commercially available ionic liquids include IL-P14 and IL-A2 (both manufactured by KOEI CHEMICAL INDUSTRY CO., LTD.); and Elegan SS-100 (manufactured by NOF CORPORATION) as a quaternary ammonium salt-based ionic liquid. The ionic liquid may be used alone or in combination of two or more.

When the treatment liquid of the present invention contains an ionic liquid, the content of the ionic liquid is preferably 0.5 to 15 mass %, more preferably 1 to 10 mass %, and even more preferably 1 to 5 mass % relative to the total mass of the treatment liquid.

<Surfactant> The treatment liquid of the present invention may also contain a surfactant. When the treatment liquid contains a surfactant, the wettability of the treatment liquid to the resist film is improved, and development and/or washing are performed more effectively. As the surfactant, the same surfactant as that which can be contained in the resist composition described later can be used. The surfactant may be used alone or in combination of two or more. When the treatment liquid of the present invention contains a surfactant, the content of the surfactant is generally 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, relative to the total mass of the treatment liquid.

<Antioxidant> The treatment liquid of the present invention may also contain an antioxidant. As the antioxidant, an amine antioxidant or a phenolic antioxidant is preferred. Antioxidants may be used alone or in combination of two or more. When the treatment liquid of the present invention contains an antioxidant, the content of the antioxidant is preferably 0.0001 to 1 mass % relative to the total mass of the treatment liquid, more preferably 0.0001 to 0.1 mass % and even more preferably 0.0001 to 0.01 mass %.

<Alkaline compound> The treatment liquid of the present invention may also contain an alkaline compound. As specific examples of alkaline compounds, compounds exemplified as acid diffusion control agents that can be contained in the inhibitor composition described later can be cited. The alkaline compound may be used alone or in combination of two or more. When the treatment liquid of the present invention contains an alkaline compound, the content of the alkaline compound is preferably 10% by mass or less, and preferably 0.5 to 5% by mass, relative to the total amount of the treatment liquid. In addition, in the present invention, the above-mentioned alkaline compound may be used alone or in combination of two or more having different chemical structures.

<Other solvents> The processing solution of the present invention may also contain other solvents. When the processing solution of the present invention is used as a developer, the processing solution of the present invention may also contain other organic solvents other than the first organic solvent and the second organic solvent. There is no particular limitation on other organic solvents, and examples thereof include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. When the processing solution of the present invention is used as a rinse solution, the processing solution of the present invention may also contain the first organic solvent and the second organic solvent. The other organic solvents are not particularly limited, and examples thereof include hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[Pattern forming method] The present invention also relates to a pattern forming method using the above-mentioned treatment solution. The pattern forming method of the present invention comprises: (i) a resist film forming step, using a resist composition to form a resist film; (ii) an exposure step, exposing the above-mentioned resist film; and (iii) a treatment step, treating the exposed resist film with the above-mentioned treatment solution.

Hereinafter, each step of the pattern forming method of the present invention will be described. Furthermore, as an example of the processing step, the developing step and the washing step will be described respectively.

[(i) Resistor film forming step] The resist film forming step is a step of forming a resist film using a resist composition, and can be performed, for example, by the following method. In order to form a resist film on a substrate using a resist composition, each component described below is dissolved in a solvent to prepare the resist composition, and after filtering with a filter as needed, it is applied to the substrate. As the pore size of the filter, the pore size is preferably 0.1 micron or less, more preferably 0.05 micron or less, and even more preferably 0.03 micron or less. As the material of the filter, polytetrafluoroethylene, polyethylene or nylon is preferred.

The resist composition is applied to a substrate (e.g., silicon, silicon dioxide coating) used in the manufacture of integrated circuit components by an appropriate coating method such as a spin coater. Afterwards, it is dried to form a resist film. Various base coating films (inorganic films, organic films, anti-reflective films) can also be formed under the resist film as needed.

As a drying method, a heating drying method is generally used. As a heating temperature, 80 to 180°C is preferred, 80 to 150°C is more preferred, 80 to 140°C is further preferred, and 80 to 130°C is particularly preferred. As a heating time, 30 to 1000 seconds is preferred, 60 to 800 seconds is more preferred, and 60 to 600 seconds is further preferred.

The thickness of the resist film is generally less than 200nm, preferably less than 100nm. For example, in order to resolve a 1:1 line and space pattern with a size of less than 30nm, the thickness of the resist film is preferably less than 50nm. As long as the film thickness is less than 50nm, it is less likely to cause pattern collapse when applying the development step described later, and better resolution performance can be obtained. From the perspective of better etching resistance and resolution, the film thickness is preferably 15 to 45nm, and 15 to 40nm is more preferred.

[(ii) Exposure step] In the pattern forming method of the present invention, the exposure method in the (ii) exposure step may also be immersion exposure. In the pattern forming method of the present invention, it is preferred to include a (iv) preheating (PB: PreBake) step before the (ii) exposure step. In the pattern forming method of the present invention, it is preferred to include a (v) post-exposure heating (PEB: Post Exposure Bake) step after the (ii) exposure step and before the (iii) development step. The pattern forming method of the present invention may also include a plurality of (ii) exposure steps. The pattern forming method of the present invention may also include a plurality of (iv) preheating steps. The pattern forming method of the present invention may also include a plurality of (v) post-exposure heating steps.

In the pattern forming method of the present invention, the above-mentioned (i) film forming step, (ii) exposure step and (iii) processing step can be performed by a well-known method. In addition, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon) and anti-reflection film) can be formed between the resist film and the support body as needed. As a material constituting the resist underlayer film, a known organic or inorganic material can be appropriately used. A protective film (top coating) can also be formed on the upper layer of the resist film. As a protective film, a known material can be appropriately used. For example, the protective film forming composition disclosed in U.S. Patent Application Publication No. 2007/0178407, U.S. Patent Application Publication No. 2008/0085466, U.S. Patent Application Publication No. 2007/0275326, U.S. Patent Application Publication No. 2016/0299432, U.S. Patent Application Publication No. 2013/0244438, and International Patent Application Publication No. 2016/157988A can be preferably used. As the protective film forming composition, one containing the above-mentioned acid diffusion control agent is preferred. The thickness of the protective film is preferably 10 to 200 nm, more preferably 20 to 100 nm, and even more preferably 40 to 80 nm.

The support for forming the resist film is not particularly limited, and in addition to the manufacturing steps of semiconductors such as ICs or the manufacturing steps of circuit substrates such as liquid crystals or thermal heads, substrates commonly used in lithography steps of other photosensitive etching processes can also be used. Specific examples of the support include inorganic substrates such as silicon, _SiO2 , and SiN.

The heating temperature in both the (iv) preheating step and the (v) post-exposure heating step is preferably 80 to 150°C, more preferably 80 to 140°C, and further preferably 80 to 130°C. The heating time in both the (iv) preheating step and the (v) post-exposure heating step is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and further preferably 60 to 600 seconds. Heating can be performed using a mechanism provided in the exposure device and the developing device, or can be performed using a heating plate, etc.

The wavelength of the light source used in the exposure step is not limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams. Among these, far ultraviolet light is preferred, and its wavelength is preferably below 250 nm, more preferably below 220 nm, and further preferably 1 to 200 nm. Specifically, it is KrF excimer laser (248 nm), ArF excimer laser (193 nm), _F2 excimer laser (157 nm), X-rays, EUV (13 nm), or electron beams, and KrF excimer laser, ArF excimer laser, EUV, or electron beams are preferred, and EUV or electron beams are more preferred.

[(iii) a step of treating the exposed film] (iii) a step of treating the exposed film generally includes: (vi) a developing step of developing with a developer (developing step); and (vii) a rinsing step of rinsing with a rinsing solution (rinsing step). The treatment solution of the present invention can be used as a developer in the developing step or as a rinsing solution in the rinsing step. Among them, it is preferably used as a rinsing solution in the rinsing step. When the treatment solution of the present invention is used as a rinsing solution in the rinsing step, it is preferably used as a developer in the developing step other than the treatment solution of the present invention.

<Developing step> The developing step is a step of developing the above-mentioned resist film after exposure by using a developer.

As developing methods, for example, there are methods of immersing the substrate in a tank filled with developer for a period of time (immersion method), methods of causing the developer to rise to the substrate surface by surface tension and remain stationary for a period of time (puddle method), methods of spraying the developer on the substrate surface (spraying method), or methods of continuously spraying the developer while scanning the developer nozzle at a certain speed on a substrate rotating at a certain speed (dynamic distribution method), etc. In addition, after the developing step, a step of stopping the developing while replacing with other solvents can also be implemented. As the developing time, it is usually 10 to 300 seconds, and 20 to 120 seconds is preferred. The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.

As the developer, the above-mentioned processing solution can be used, and other developer solutions can also be used. It is preferred to use other developer solutions. In addition to development using the processing solution, development can also be performed using an alkaline developer solution (so-called double development).

(Other developers) Other developers are described below. The vapor pressure of the organic solvent used in the developer (the overall vapor pressure in the case of a mixed solvent) is preferably 5 kPa or less at 20°C, more preferably 3 kPa or less, and even more preferably 2 kPa or less. By setting the vapor pressure of the organic solvent to 5 kPa or less, the evaporation of the developer on the substrate or in the developer cup is suppressed, the temperature uniformity within the substrate surface is improved, and as a result, the dimensional uniformity within the substrate surface becomes good. The organic solvent used as the developer is not particularly limited, and examples thereof include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, and the like.

The developer preferably contains one or more solvents selected from ketone solvents, ester solvents, alcohol solvents and ether solvents.

Examples of the ester solvent include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, propyl acetate, isopropyl acetate, amyl acetate (pentyl acetate), isoamyl acetate (isopentyl acetate), 3-methylbutyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, isohexyl acetate, heptyl acetate, octyl acetate, methoxyethyl acetate, ethoxyethyl acetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono phenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxybutyl acetate oxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, pentyl propionate, hexyl propionate Ester, heptyl propionate, butyl butyrate, isobutyl butyrate, amyl butyrate, hexyl butyrate, isobutyl isobutyrate, propyl valerate, isopropyl valerate, butyl valerate, amyl valerate, ethyl hexanoate, propyl hexanoate, butyl hexanoate, isobutyl hexanoate, methyl heptanoate, ethyl heptanoate, propyl heptanoate, cyclohexyl acetate, cycloheptyl acetate, 2-ethylhexyl acetate, cyclopentyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate and propyl-3-methoxypropionate, etc. Among them, butyl acetate, pentyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate or butyl butyrate is preferred, and isoamyl acetate is more preferred.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, propiophenone, methyl ethyl ketone, methylisobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetone alcohol, acetylmethanol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate and γ-butyrolactone, with 2-heptanone being preferred.

Examples of the alcohol solvent include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-decanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, 3-methyl-3-pentanol, cyclopentanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, 5-methyl-2-hexanol, 4 -methyl-2-hexanol, 4,5-dimethyl-2-hexanol, 6-methyl-2-heptanol, 7-methyl-2-octanol, 8-methyl-2-nonanol, 9-methyl-2-decanol and 3-methoxy-1-butanol and other alcohols (monovalent alcohols); glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; glycol ether solvents containing a hydroxyl group such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol), diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, etc., and glycol ether solvents are preferred.

As the ether solvent, for example, in addition to the glycol ether solvent containing the above-mentioned hydroxyl group, there can be listed glycol ether solvents not containing a hydroxyl group such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, aromatic ether solvents such as anisole and phenethyl ether, dihydrofuran, tetrahydrofuran, tetrahydropyran, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-hydrofuran, and isopropyl ether, etc. Among them, glycol ether solvents and aromatic ether solvents such as anisole are preferred.

Examples of the amide solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphotricarboxylic acid, and 1,3-dimethyl-2-imidazolidinone.

Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents such as pentane, hexane, octane, nonane, decane, dodecane, undecane, hexadecane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, perfluorohexane, and perfluoroheptane; and aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, and dipropylbenzene. In addition, unsaturated hydrocarbon solvents can also be used as hydrocarbon solvents, for example, unsaturated hydrocarbon solvents such as octene, nonene, decene, undecene, dodecene, and hexadecene can be listed. The number of double bonds or triple bonds possessed by the unsaturated hydrocarbon solvent is not particularly limited, and can be located at any position of the hydrocarbon chain. Moreover, when the unsaturated hydrocarbon solvent has a double bond, it can also exist as a mixture of cis-isomers and trans-isomers. In addition, the aliphatic hydrocarbon solvent as the hydrocarbon solvent can also be a mixture of compounds with the same carbon number and different structures. For example, when decane is used as the aliphatic hydrocarbon solvent, 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane and isooctane, which are compounds with the same carbon number and different structures, can also be included in the aliphatic hydrocarbon solvent. Moreover, the above-mentioned compounds with the same carbon number and different structures can contain only one kind, or can contain multiple kinds as described above.

From the perspective of being able to further suppress swelling of the resist film when EUV light and electron beams are used in the above exposure step, an ester solvent having a carbon number of 6 or more (preferably 6 to 14, more preferably 6 to 12, and even more preferably 6 to 10) and a number of impurities of 2 or less is preferred as a developer. As the impurity atom, any atom other than carbon and hydrogen atoms may be used, such as oxygen atoms, nitrogen atoms, and sulfur atoms. It is preferred that the number of impurities is 2 or less. Specific examples of the ester solvent having 6 or more carbon atoms and 2 or less heteroatoms include butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, amyl propionate, hexyl propionate, heptyl propionate, butyl butyrate, butyl isobutyrate and isobutyl isobutyrate, and isoamyl acetate or butyl isobutyrate is more preferred.

From the perspective of further suppressing swelling of the resist film when EUV light and electron beam are used in the above-mentioned exposure step, a mixed solvent of an ester solvent and a hydrocarbon solvent or a mixed solvent of a ketone solvent and a hydrocarbon solvent may be used as a developer instead of the above-mentioned ester solvent having a carbon number of 6 or more and a impurity number of 2 or less.

The content of the hydrocarbon solvent in the above-mentioned mixed solvent depends on the solvent solubility of the resist film and is therefore not particularly limited. It only needs to be properly prepared to determine the required amount.

Among the mixed solvents of ester solvents and hydrocarbon solvents, isoamyl acetate is preferred as the ester solvent. From the viewpoint of easy adjustment of the solubility of the resist film, a saturated hydrocarbon solvent (for example, nonane, octane, decane, dodecane, undecane, hexadecane, etc.) is preferred as the hydrocarbon solvent.

In the mixed solvent of the ketone solvent and the hydrocarbon solvent, as the ketone solvent, for example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, 2,5-dimethyl-4-hexanone, cyclohexanone, methylcyclohexanone, propiophenone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetone alcohol, acetylmethanol, acetophenone, methylnaphthyl ketone, isophorone and propylene carbonate, and diisobutyl ketone or 2,5-dimethyl-4-hexanone is preferred. From the viewpoint of easily adjusting the solubility of the resist film, a saturated hydrocarbon solvent (for example, nonane, octane, decane, dodecane, undecane, hexadecane, etc.) is preferred as the hydrocarbon solvent.

The above solvents may be mixed in multiple forms, or may be mixed with solvents other than the above or water. The overall water content of the developer is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water. The content of the organic solvent relative to the total amount of the developer is preferably 50-100% by mass, more preferably 80-100% by mass, even more preferably 90-100% by mass, and particularly preferably 95-100% by mass.

The developer may also contain an appropriate amount of a known surfactant as required.

The content of the surfactant relative to the total amount of the developer is generally 0.001 to 5 mass %, preferably 0.005 to 2 mass %, and more preferably 0.01 to 0.5 mass %.

The developer may also contain an alkaline compound. Specific examples of the alkaline compound include the compounds exemplified as the acid diffusion control agent that can be contained in the inhibitor composition described later.

As an organic solvent used as a developer, in addition to the above-mentioned ester solvents, ester solvents represented by the following general formula (S1) or the following general formula (S2) are also preferred. As the above-mentioned ester solvent, the ester solvent represented by the general formula (S1) is more preferred, alkyl acetate is further preferred, and butyl acetate, amyl acetate (pentyl acetate) (pentyl acetate) (pentyl acetate) or isoamyl acetate (isopentyl acetate) (isopentyl acetate) (isopentyl acetate) is particularly preferred.

R-C(=O)-O-R’ General formula (S1)

In the general formula (S1), R and R' independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom. R and R' may also be bonded to each other to form a ring. The carbon number of the alkyl group, alkoxy group and alkoxycarbonyl group represented by R and R' is preferably 1 to 15, and the carbon number of the cycloalkyl group is preferably 3 to 15. The alkyl group, cycloalkyl group, alkoxy group and alkoxycarbonyl group represented by R and R', and the ring formed by R and R' bonding to each other may also have a substituent. There is no particular limitation on the substituent, and examples thereof include a hydroxyl group, a group containing a carbonyl group (for example, an acyl group, an aldehyde group and an alkoxycarbonyl group, etc.) and a cyano group. As R and R', a hydrogen atom or an alkyl group is preferred.

Examples of the solvent represented by the general formula (S1) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, and ethyl 2-hydroxypropionate.

Among them, unsubstituted alkyl groups are preferred as R and R'. As the solvent represented by general formula (S1), alkyl acetate is preferred, butyl acetate, amyl acetate (pentyl acetate) or isoamyl acetate (isoamyl acetate) is more preferred, and isoamyl acetate is further preferred.

When the developer contains the solvent represented by the general formula (S1), the developer may further contain one or more other organic solvents (hereinafter also referred to as "co-solvents"). As the co-solvent, there is no particular limitation as long as it can be mixed in the solvent represented by the general formula (S1) without separation. Examples of the co-solvent include solvents selected from ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents and hydrocarbon solvents other than the solvent represented by the general formula (S1). The co-solvent may be one or two. From the perspective of obtaining stable performance, one is preferred. When the developer is a mixed solvent of the solvent represented by the general formula (S1) and a co-solvent, the mixing ratio of the solvent represented by the general formula (S1) and the co-solvent is generally 20:80 to 99:1, preferably 50:50 to 97:3, more preferably 60:40 to 95:5, and even more preferably 60:40 to 90:10, by mass ratio.

As the organic solvent used as the developer, the solvent represented by the following general formula (S2) is also preferred.

R’’-C（=O）-O-R’’’-O-R’’’’ General formula (S2)

In the general formula (S2), R'' and R'''' independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom. R'' and R'''' may be bonded to each other to form a ring. As R'' and R'''', a hydrogen atom or an alkyl group is preferred. As the carbon number of the alkyl group, alkoxy group and alkoxycarbonyl group represented by R'' and R'''', 1 to 15 is preferred, and as the carbon number of the cycloalkyl group, 3 to 15 is preferred. R''' represents an alkylene group or a cycloalkylene group, and an alkylene group is preferred. As the carbon number of the alkylene group represented by R''', 1 to 10 is preferred, and as the carbon number of the cycloalkylene group represented by R''', 3 to 10 is preferred. In addition, the alkylene group represented by R''' may also have an ether bond in the alkylene chain. The alkylene group, cycloalkyl group, alkoxy group and alkoxycarbonyl group represented by R'' and R'''', the alkylene group and cycloalkylene group represented by R''', and the ring formed by R'' and R'''' bonding to each other may also have a substituent. There is no particular limitation on the substituent, and examples thereof include groups including hydroxyl groups, carbonyl groups (for example, acyl groups, aldehyde groups and alkoxycarbonyl groups, etc.) and cyano groups, etc.

Examples of the solvent represented by the general formula (S2) include propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, ethyl methoxyacetate, ethyl ethoxyacetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate and 4-methyl-4-methoxypentyl acetate, etc. Propylene glycol monomethyl ether acetate is preferred. Among them, R'' and R'''' are unsubstituted alkyl groups, preferably R''' is unsubstituted alkylene groups, more preferably R'' and R'''' are methyl groups and ethyl groups, and even more preferably R'' and R'''' are methyl groups.

When the developer contains the solvent represented by the general formula (S2), the developer may further contain one or more other organic solvents (hereinafter also referred to as "co-solvents"). As the co-solvent, there is no particular limitation as long as it can be mixed in the solvent represented by the general formula (S2) without separation. Examples of the co-solvent include solvents selected from ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents and hydrocarbon solvents other than the solvent represented by the general formula (S2). The co-solvent may be one or two. From the perspective of obtaining stable performance, one is preferred. When the developer is a mixed solvent of the solvent represented by the general formula (S2) and a co-solvent, the mixing ratio of the solvent represented by the general formula (S2) and the co-solvent is generally 20:80 to 99:1, preferably 50:50 to 97:3, more preferably 60:40 to 95:5, and even more preferably 60:40 to 90:10, by mass ratio.

Furthermore, as the organic solvent used as the developer, an ether solvent containing one or more aromatic rings is also preferred, the solvent represented by the following general formula (S3) is more preferred, and anisole is further preferred.

[Chemical formula 1]

In the general formula (S3), _RS represents an alkyl group. The alkyl group preferably has 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

(Rinsing step) The washing step is a step of washing (rinsing) with a washing liquid after the above-mentioned developing step.

In the rinsing step, the developed substrate is cleaned using the above-mentioned rinsing liquid. The cleaning method is not particularly limited, and can be applied to, for example, a method of continuously spraying the rinsing liquid on a substrate rotating at a certain speed (rotational spraying method), a method of immersing the substrate in a tank filled with the rinsing liquid for a period of time (immersion method), a method of spraying the rinsing liquid onto the surface of the substrate (spraying method), etc. Among them, it is preferable to use the rotational spraying method for cleaning, and after cleaning, the substrate is rotated at a speed of 2000rpm to 4000rpm to remove the rinsing liquid from the substrate. The rinsing time is usually 10 seconds to 300 seconds, preferably 10 seconds to 180 seconds, and more preferably 20 seconds to 120 seconds. The temperature of the rinsing liquid is preferably 0 to 50°C, and more preferably 15 to 35°C.

Furthermore, after the development process or the rinsing process, the developer or rinse solution attached to the pattern can be removed by a supercritical fluid. Moreover, after the development process, the rinse process or the process based on the supercritical fluid, a drying process can be performed to remove the solvent remaining in the pattern. The drying temperature is usually 40 to 160°C, preferably 50 to 150°C, and more preferably 50 to 110°C. The drying time is usually 15 to 300 seconds, preferably 15 to 180 seconds.

In the pattern forming method of the present invention, the processing liquid of the present invention is used as at least one of a developer and a rinser, and it is preferred that the processing liquid of the present invention is used as a rinser.

For example, when pattern formation is performed by using an ester solvent as a developer in the developing step and the processing solution of the present invention as a rinse solution in the rinse step, it is preferable to set the interval between supplying the developer and the rinse solution to the exposed resist film to 1 second or more. By setting the supply interval of the developer and the rinse solution to a predetermined time or more, the deterioration of the solubility of the unexposed area of the exposed resist film can be suppressed, and the increase of defects caused by the solvent casting method can be suppressed.

In addition, usually the developer and rinse solution are stored in a common waste tank through piping after use. In this case, if an ester solvent is used as the developer in the development step and the treatment solution of the present invention is used as the rinse solution in the rinse step, the resist dissolved in the developer will precipitate and adhere to the back of the substrate and the side of the piping, etc., which may cause contamination of the device. In order to solve the above problem, there is a method of passing the solvent that dissolves the resist through the piping again. As the method of passing through the piping, there can be listed a method of washing the back or side of the substrate with the solvent that dissolves the resist and then flowing out, and a method of flowing out through the piping without contacting the resist with the solvent that dissolves the resist. The solvent passing through the pipe is not particularly limited as long as it can dissolve the inhibitor, and for example, the organic solvent used as the above-mentioned developer can be listed. Specifically, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-heptanone, ethyl lactate, 1-propanol, acetone, etc. Among them, PGMEA, PGME or cyclohexanone is preferred.

Furthermore, as other methods for solving the above-mentioned problems, in order to prevent precipitation of the resistor in the waste liquid flowing into the waste liquid tank through the piping after use, there can be listed a method of adjusting the amount ratio of the developer and the rinse liquid discharged into the piping after use to an amount ratio that does not cause precipitation of the resistor, and a method of further mixing a solvent with high solubility in the resistor into the developer and the rinse liquid discharged into the piping after use. As a specific method, for example, an organic solvent having a higher SP value than the first organic solvent contained in the processing liquid of the present invention is continuously supplied to the back side of the wafer between the developing step and the rinse step, thereby suppressing precipitation/precipitation of the resistor in the waste liquid flowing into the waste liquid tank through the piping after use.

Furthermore, it is also preferable that the developer and the rinse solution are stored in different waste liquid tanks after use. For example, when pattern formation is performed by using an ester solvent as the developer in the development step and the processing liquid of the present invention as the rinse solution in the rinse step, if they are stored in the same waste liquid tank through piping after use, the components contained in the resist composition such as the resin dissolved in the developer will precipitate (precipitate/solidify), which may cause device contamination. Specifically, the precipitated components not only cause blockage of the waste liquid piping, but also contamination in the processing chamber. In order to solve the above problem, it is preferable that the developer and the rinse solution are stored in different waste liquid tanks after use by replacing the piping or replacing the processing chamber. Furthermore, in order to remove the resist components that may be attached to the processing chamber, it is preferred to clean the interior of the processing chamber after the processing is completed using a solvent having a higher SP value than the first organic solvent contained in the processing solution of the present invention.

[Resist composition] Next, a resist composition that is preferably used in combination with the treatment solution of the present invention is described in detail.

<Resin (A)> The resist composition contains a resin whose polarity increases when decomposed by the action of an acid (hereinafter, also referred to as "acid-decomposable resin" or "resin (A)"). That is, in the pattern forming method of the present invention, typically, when an alkaline developer is used as a developer, a positive pattern is preferably formed, and when an organic developer is used as a developer, a negative pattern is preferably formed. The resin (A) usually contains a group whose polarity increases when decomposed by the action of an acid (hereinafter, also referred to as "acid-decomposable group"), and preferably contains a repeating unit having an acid-decomposable group.

《Repeating units with acid-decomposable groups》 An acid-decomposable group refers to a group that generates a polar group by decomposing it under the action of an acid. It is preferred that the acid-decomposable group has a structure in which the polar group is protected by a dissociative group that is dissociated by the action of an acid. That is, the resin (A) has a repeating unit having a group that generates a polar group by decomposing it under the action of an acid. The polarity of the resin having the repeating unit increases under the action of an acid, thereby increasing its solubility relative to an alkaline developer and decreasing its solubility relative to an organic solvent. As polar groups, alkali-soluble groups are preferred, for example, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, phosphoric acid groups, sulfonamide groups, sulfonyl imide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imide groups, bis (alkylcarbonyl) methylene groups, bis (alkylcarbonyl) imide groups, bis (alkylsulfonyl) methylene groups, bis (alkylsulfonyl) imide groups, tris (alkylcarbonyl) methylene groups, tris (alkylsulfonyl) methylene groups, and alcoholic hydroxyl groups. Among them, as polar groups, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups) or sulfonic acid groups are preferred.

Examples of the dissociating group that is dissociated by the action of an acid include groups represented by formulae (Y1) to (Y4). Formula (Y1): -C(Rx ₁ )(Rx ₂ )(Rx ₃ ) Formula (Y2): -C(=O)OC(Rx ₁ )(Rx ₂ )(Rx ₃ ) Formula (Y3): -C(R ₃₆ )(R ₃₇ )(OR ₃₈ ) Formula (Y4): -C(Rn)(H)(Ar)

In formula (Y1) and formula (Y2), Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched) or an aryl group (monocyclic or polycyclic). In addition, when Rx ₁ to Rx ₃ are all alkyl groups (linear or branched), it is preferred that at least two of Rx ₁ to Rx ₃ are methyl groups. It is preferred that Rx ₁ to Rx ₃ each independently represent a linear or branched alkyl group, and it is more preferred that Rx ₁ to Rx ₃ each independently represent a linear alkyl group. Two of Rx ₁ to Rx ₃ may be bonded to form a monocyclic or polycyclic ring. As the alkyl group of Rx ₁ to Rx ₃ , alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl, are preferred. As the cycloalkyl group of Rx ₁ to Rx ₃ , monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl are preferred. As the aryl group of Rx ₁ to Rx ₃ , aryl groups having 6 to 10 carbon atoms are preferred, for example, phenyl, naphthyl and anthracenyl can be mentioned. As the alkenyl group of Rx ₁ to Rx ₃ , vinyl is preferred. As the ring formed by two groups of Rx ₁ to Rx ₃ being bonded, cycloalkyl is preferred. As the cycloalkyl group formed by two of Rx ₁ to Rx ₃ being bonded together, a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl or adamantyl is preferred, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. The cycloalkyl group formed by two of Rx ₁ to Rx ₃ being bonded together may be a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group, or may be substituted with a vinylene group. In addition, the cycloalkyl groups may be a group having one or more of the ethylene groups constituting the cycloalkane substituted with a vinylene group. The group represented by formula (Y1) or formula (Y2) is preferably in a form where _Rx1 is a methyl group or an ethyl group and _Rx2 and _Rx3 are bonded to form the above-mentioned cycloalkyl group.

In formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may also be bonded to each other to form a ring. Examples of the monovalent organic group include alkyl, cycloalkyl, aryl, aralkyl and alkenyl groups. It is also preferred that R ₃₆ is a hydrogen atom. In addition, the above-mentioned alkyl, cycloalkyl, aryl and aralkyl groups may also include groups having heteroatoms such as oxygen atoms and/or heteroatoms such as carbonyl groups. For example, the above-mentioned alkyl, cycloalkyl, aryl and aralkyl groups may be groups in which one or more of the methylene groups is substituted by a heteroatoms such as oxygen atoms and/or heteroatoms such as carbonyl groups. In addition, R ₃₈ may be bonded to each other with another substituent group possessed by the main chain of the repeating unit to form a ring. The group formed by R ₃₈ and another substituent of the main chain of the repeating unit bonding to each other is preferably an alkylene group such as methylene.

As the formula (Y3), a group represented by the following formula (Y3-1) is preferred.

[Chemical formula 2]

Here, _L1 and _L2 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining these (for example, a group formed by combining an alkyl group and an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group that may contain a heteroatom, a cycloalkyl group that may contain a heteroatom, an aryl group that may contain a heteroatom, an amino group, an ammonium group, an alkyl group, a cyano group, an aldehyde group, or a group formed by combining these (for example, a group formed by combining an alkyl group and a cycloalkyl group). The alkyl group and the cycloalkyl group may also be a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group, for example, in one of the methylene groups. In addition, it is preferred that one of _L1 and _L2 is a hydrogen atom and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining an alkyl group and an aryl group. At least two of Q, M and _L1 may be bonded to form a ring (preferably a 5-membered or 6-membered ring). From the viewpoint of pattern refinement, _L2 is preferably a di- or tertiary alkyl group, and a tertiary alkyl group is more preferably. Examples of di-alkyl groups include isopropyl, cyclohexyl or norbornyl, and examples of tertiary alkyl groups include t-butyl or adamantyl. In such forms, Tg (glass transition temperature) and activation energy become high, so that film strength can be ensured while suppressing rusting.

In formula (Y4), Ar represents an aromatic cyclic group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and Ar may also be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

From the viewpoint of excellent acid decomposability of the repeating unit, when a non-aromatic ring is directly bonded to the polar group (or its residue) in the free group protecting the polar group, it is also preferred that the ring member atom adjacent to the ring member atom directly bonded to the polar group (or its residue) in the non-aromatic ring does not have a halogen atom such as a fluorine atom as a substituent.

The dissociated group to be dissociated by the action of an acid may be a 2-cyclopropenyl group having a substituent (such as an alkyl group) such as a 3-methyl-2-cyclopropenyl group, or a cyclohexyl group having a substituent (such as an alkyl group) such as a 1,1,4,4-tetramethylcyclohexyl group.

As the repeating unit having an acid-decomposable group, a repeating unit represented by formula (A) is also preferred.

[Chemical formula 3]

L ₁ represents a divalent linking group which may have a fluorine atom or an iodine atom, R ₁ represents an alkyl group which may have a hydrogen atom, a fluorine atom, an iodine atom, a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom, and R ₂ represents a dissociating group which may have a fluorine atom or an iodine atom and which is dissociated by the action of an acid. At least one of L ₁ , R ₁ and R ₂ has a fluorine atom or an iodine atom. L ₁ represents a divalent linking group which may have a fluorine atom or an iodine atom. Examples of the divalent linking group which may have a fluorine atom or an iodine atom include -CO-, -O-, -S-, -SO-, -SO ₂ -, a alkyl group which may have a fluorine atom or an iodine atom (for example, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, etc.), and a linking group formed by connecting a plurality of these groups. Among them, as L ₁ , -CO- or -arylene-alkylene-having fluorine atom or iodine atom is preferred. As the arylene, phenylene is preferred. The alkylene may be linear or branched. The carbon number of the alkylene is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. The total number of fluorine atoms and iodine atoms contained in the alkylene having fluorine atom or iodine atom is not particularly limited, but 2 or more is preferred, 2 to 10 is more preferred, and 3 to 6 is further preferred.

_R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. The alkyl group may be a straight chain or a branched chain. The carbon number of the alkyl group is not particularly limited, and 1 to 10 are preferred, and 1 to 3 are more preferred. The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom is not particularly limited, and 1 or more is preferred, 1 to 5 are more preferred, and 1 to 3 are further preferred. The above-mentioned alkyl group may also contain miscellaneous atoms such as oxygen atoms other than halogen atoms.

_R2 represents a dissociating group which dissociates by the action of an acid and which may have a fluorine atom or an iodine atom. Examples of the dissociating group include groups represented by formulae (Z1) to (Z4). Formula (Z1): -C( _Rx11 )( _Rx12 )( _Rx13 ) Formula (Z2): -C(=O)OC( _Rx11 )( _Rx12 )( _Rx13 ) Formula (Z3): -C( _R136 )( _R137 )( _OR138 ) Formula (Z4): -C( _Rn1 )(H)( _Ar1 )

In formula (Z1) and (Z2), _Rx11 to _Rx13 independently represent an alkyl group (linear or branched) which may have a fluorine atom or an iodine atom, a cycloalkyl group (monocyclic or polycyclic) which may have a fluorine atom or an iodine atom, an alkenyl group (linear or branched) which may have a fluorine atom or an iodine atom, or an aryl group (monocyclic or polycyclic) which may have a fluorine atom or an iodine atom. When all of _Rx11 to _Rx13 are alkyl groups (linear or branched), it is preferred that at least two of _Rx11 to _Rx13 are methyl groups. _Rx11 to _Rx13 are the same as _Rx1 to _Rx3 in (Y1) and (Y2) above, except that they may have a fluorine atom or an iodine atom, and have the same definitions and preferred ranges as for alkyl, cycloalkyl, alkenyl and aryl groups.

In formula (Z3), R ₁₃₆ to R ₁₃₈ each independently represent a hydrogen atom, or a monovalent organic group that may have a fluorine atom or an iodine atom. R ₁₃₇ and R ₁₃₈ may also be bonded to each other to form a ring. Examples of the monovalent organic group that may have a fluorine atom or an iodine atom include an alkyl group that may have a fluorine atom or an iodine atom, a cycloalkyl group that may have a fluorine atom or an iodine atom, an aryl group that may have a fluorine atom or an iodine atom, an aralkyl group that may have a fluorine atom or an iodine atom, and a group formed by combining these groups (for example, a group formed by combining an alkyl group and a cycloalkyl group). In addition, the above-mentioned alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom in addition to a fluorine atom and an iodine atom. That is, the above-mentioned alkyl group, cycloalkyl group, aryl group, and aralkyl group may be a group in which, for example, one of the methylene groups is substituted by a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. Furthermore, _R138 may also bond with another substituent of the main chain of the repeating unit to form a ring. In this case, the group formed by bonding _R138 and another substituent of the main chain of the repeating unit is preferably an alkylene group such as a methylene group.

As the formula (Z3), a group represented by the following formula (Z3-1) is preferred.

[Chemical formula 4]

Here, L ₁₁ and L ₁₂ each independently represent a hydrogen atom; an alkyl group which may have a heteroatom selected from a fluorine atom, an iodine atom, and an oxygen atom; a cycloalkyl group which may have a heteroatom selected from a fluorine atom, an iodine atom, and an oxygen atom; an aryl group which may have a heteroatom selected from a fluorine atom, an iodine atom, and an oxygen atom; or a group formed by combining these (for example, a group formed by combining an alkyl group and a cycloalkyl group which may have a heteroatom selected from a fluorine atom, an iodine atom, and an oxygen atom). M ₁ represents a single bond or a divalent linking group. _Q1 represents an alkyl group which may have a heteroatom selected from a fluorine atom, an iodine atom and an oxygen atom; a cycloalkyl group which may have a heteroatom selected from a fluorine atom, an iodine atom and an oxygen atom; an aryl group selected from a fluorine atom, an iodine atom and an oxygen atom; an amino group; an ammonium group; an oxalyl group; a cyano group; an aldehyde group; or a group formed by combining these (for example, a group formed by combining an alkyl group which may have a heteroatom selected from a fluorine atom, an iodine atom and an oxygen atom and a cycloalkyl group).

In formula (Y4), Ar ₁ represents an aromatic cyclic group which may have a fluorine atom or an iodine atom. Rn ₁ represents an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. Rn ₁ and Ar ₁ may also be bonded to each other to form a non-aromatic ring.

As the repeating unit having an acid-decomposable group, a repeating unit represented by the general formula (AI) is also preferred.

[Chemical formula 5]

In the general 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. _Rx1 to _Rx3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aromatic group (monocyclic or polycyclic). Among them, when _Rx1 to _Rx3 are all alkyl groups (linear or branched), it is preferred that at least two of _Rx1 to _Rx3 are methyl groups. Two of _Rx1 to _Rx3 may also be bonded to form a monocyclic or polycyclic group (monocyclic or polycyclic cycloalkyl group, etc.).

Examples of the alkyl group which may have a substituent represented by _Xa1 include a methyl group or a group represented by _-CH2 -R11 _{. R11 represents} a halogen atom (fluorine atom, etc.), a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms which may be substituted by a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted by a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted by a halogen atom. An alkyl group having 3 or less carbon atoms is preferred, and a methyl group is more preferred. _Xa1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

As the divalent linking group of T, there can be mentioned an alkylene group, an aromatic cyclic group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH ₂ - group, a -(CH ₂ ) ₂ - group, or a -(CH ₂ ) ₃ - group.

As the alkyl group of Rx ₁ to Rx ₃ , alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl, are preferred. As the cycloalkyl group of Rx ₁ to Rx ₃ , monocyclic cycloalkyl groups, such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups, such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl, are preferred. As the aryl group of Rx ₁ to Rx ₃ , aryl groups having 6 to 10 carbon atoms are preferred, for example, phenyl, naphthyl and anthracenyl, etc. are listed. As the alkenyl group of Rx ₁ to Rx ₃ , vinyl is preferred. As the cycloalkyl group formed by two of Rx ₁ to Rx ₃ being bonded together, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl are preferred, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl are preferred. Among them, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred. The cycloalkyl group formed by two of Rx ₁ to Rx ₃ being bonded together may be, for example, one of the methylene groups constituting the ring may be substituted by a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group, or may be substituted by a vinylene group. Furthermore, the cycloalkyl groups may be, for example, one or more of the ethylene groups constituting the cycloalkane may be substituted by a vinylene group. In the repeating unit represented by the general formula (AI), for example, _Rx1 is a methyl group or an ethyl group, and _Rx2 and _Rx3 are bonded to form the above-mentioned cycloalkyl group.

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

The repeating unit represented by the general formula (AI) is preferably an acid-decomposable tertiary alkyl (meth)acrylate repeating unit (a repeating unit in which _Xa1 represents a hydrogen atom or a methyl group and T represents a single bond).

The content of the repeating unit having an acid-decomposable group is preferably 15 mol% or more, more preferably 20 mol% or more, further preferably 25 mol% or more, and particularly preferably 30 mol% or more, based on the total repeating units in the resin (A). The upper limit is not particularly limited, but is preferably 90 mol% or less, more preferably 80 mol% or less, and further preferably 70 mol%.

Specific examples of repeating units having an acid-decomposable group are shown below, but the present invention is not limited thereto. In the formula, _Xa1 represents any one of H, _CH3 , _CF3 and _CH2OH , or Rxa and Rxb each represent a linear or branched alkyl group having 1 to 5 carbon atoms.

[Chemical formula 6]

[Chemical formula 7]

[Chemical formula 8]

[Chemical formula 9]

[Chemical formula 10]

The resin (A) may also contain repeating units other than the above-mentioned repeating units. For example, the resin (A) may also contain at least one repeating unit selected from the group including the following Group A and/or at least one repeating unit selected from the group including the following Group B. Group A: A group including the repeating units (20) to (29) below. (20) The repeating unit described below having an acid group (21) The repeating unit described below having a fluorine atom or an iodine atom (22) The repeating unit described below having a lactone group, a sultone group or a carbonate group (23) The repeating unit described below having a photoacid generating group (24) The repeating unit represented by the general formula (V-1) described below or the general formula (V-2) described below (25) The repeating unit represented by the formula (A) described below (26) The repeating unit represented by the formula (B) described below (27) The repeating unit represented by the formula (C) described below (28) The repeating unit represented by the formula (D) described below (29) The repeating unit represented by the formula (E) described below Group B: A group comprising the repeating units of (30) to (32) below. (30) The following repeating unit having at least one group selected from lactone group, sultone group, carbonate group, hydroxyl group, cyano group and alkali-soluble group (31) The following repeating unit having an alicyclic hydrocarbon structure and not showing acid decomposition (32) The following repeating unit represented by the general formula (III) having neither hydroxyl group nor cyano group

When the resist composition is used for EUV purposes, the resin (A) preferably has at least one repeating unit selected from the group including the above-mentioned group A. In addition, when the resist composition is used for EUV purposes, the resin (A) preferably contains at least one of a fluorine atom and an iodine atom. When the resin (A) contains both a fluorine atom and an iodine atom, the resin (A) may have one repeating unit containing both a fluorine atom and an iodine atom, and the resin (A) may also contain both a repeating unit containing a fluorine atom and a repeating unit containing an iodine atom. In addition, when the resist composition is used for EUV purposes, the resin (A) preferably has a repeating unit containing an aromatic group. When the resist composition is used for ArF purposes, the resin (A) preferably has at least one repeating unit selected from the group including the above-mentioned group B. In addition, when the resist composition is used for ArF purposes, the resin (A) preferably does not contain any of fluorine atoms and silicon atoms. In addition, when the composition is used for ArF purposes, the resin (A) preferably does not have an aromatic group.

《Repeating units with acid groups》 The resin (A) may also have repeating units with acid groups. As the acid group, an acid group with a pKa of 13 or less is preferred. As the acid group, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group or an isopropanol group is preferred. Furthermore, the above-mentioned hexafluoroisopropanol group may be a group in which one or more (preferably 1 to 2) of the fluorine atoms are replaced by a group other than a fluorine atom (such as an alkoxycarbonyl group). The -C(CF ₃ )(OH)-CF ₂ - formed in this way is preferred as the acid group. Furthermore, a ring containing -C(CF ₃ )(OH)-CF ₂ - may be formed in which one or more fluorine atoms are replaced by a group other than a fluorine atom. The repeating unit having an acid group is preferably a repeating unit having a structure in which a polar group is released by the action of the acid and is different from a repeating unit having a lactone group, a sultone group or a carbonate group described later.

The repeating unit having an acid group may also have a fluorine atom or an iodine atom.

As the repeating unit having an acid group, a repeating unit represented by formula (B) is preferred.

[Chemical formula 11]

R ₃ represents a hydrogen atom, or a monovalent organic group which may have a fluorine atom or an iodine atom. As the monovalent organic group which may have a fluorine atom or an iodine atom, a group represented by -L ₄ -R ₈ is preferred. L ₄ represents a single bond or an ester group. As R ₈ , an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group composed of these groups can be cited.

_R4 and _R5 each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group which may have a fluorine atom or an iodine atom.

_L2 represents a single bond or an ester group. _L3 represents an (n+m+1)-valent aromatic hydrocarbon ring group or an (n+m+1)-valent alicyclic hydrocarbon ring group. Examples of the aromatic hydrocarbon ring group include a benzene ring group and a naphthyl ring group. The alicyclic hydrocarbon ring group may be a monocyclic group or a polycyclic group, for example, a cycloalkyl ring group. _R6 represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). In addition, when _R6 is a hydroxyl group, _L3 is preferably an (n+m+1)-valent aromatic hydrocarbon ring group. _R7 represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. m represents an integer greater than 1. m is preferably an integer of 1 to 3, more preferably an integer of 1 to 2. n represents an integer of 0 or 1 or more. n is preferably an integer of 1 to 4. In addition, (n+m+1) is preferably an integer of 1 to 5.

As the repeating unit having an acid group, a repeating unit represented by the following general formula (I) is also preferred.

[Chemical formula 12]

In the general formula (I), R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ may also form a ring by bonding with Ar ₄ , in which case R ₄₂ represents a single bond or an alkylene group. X ₄ represents a single bond, -COO- or -CONR ₆₄ -, and R ₆₄ represents a hydrogen atom or an alkylene group. L ₄ represents a single bond or an alkylene group. Ar ₄ represents an (n+1)-valent aromatic cyclic group, and when bonding with R ₄₂ to form a ring, represents an (n+2)-valent aromatic cyclic group. n represents an integer of 1 to 5.

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

The cycloalkyl group of R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I) may be a monocyclic group or a polycyclic group. Among them, a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group is preferred. The halogen atom of R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I) may be a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred. The alkyl group included in the alkoxycarbonyl group of R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I) is preferably the same as the alkyl group in R ₄₁ , R ₄₂ and R ₄₃ mentioned above.

Preferred substituents in the above groups include, for example, alkyl, cycloalkyl, aryl, amino, amide, urea, carbamate, hydroxyl, carboxyl, halogen, alkoxy, sulfide, acyl, acyloxy, alkoxycarbonyl, cyano, and nitro. The substituent preferably has 8 or less carbon atoms.

Ar ₄ represents an (n+1)-valent aromatic cyclic group. The divalent aromatic cyclic group when n is 1 is preferably an aryl group having 6 to 18 carbon atoms such as phenylene, toluene, naphthyl and anthracene, or a divalent aromatic cyclic group containing a heterocyclic ring such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a trioxane ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring and a thiazole ring. The above aromatic cyclic group may also have a substituent.

As a specific example of an (n+1)-valent aromatic ring group when n is an integer greater than 2, a group formed by removing (n-1) arbitrary hydrogen atoms from the above-mentioned specific example of a divalent aromatic ring group is preferred. The (n+1)-valent aromatic ring group may further have a substituent.

Examples of the substituents that the alkyl, cycloalkyl, alkoxycarbonyl, alkylene and (n+1)-valent aromatic ring groups may have include the alkyl groups listed in R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I), alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy; and aryl groups such as phenyl. Examples of the alkyl group of R ₆₄ in -CONR ₆₄ - (R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₄ include alkyl groups having 20 or less carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl. Alkyl groups having 8 or less carbon atoms are preferred. X ₄ is preferably a single bond, -COO- or -CONH-, and more preferably a single bond or -COO-.

As the alkylene group in L ₄ , an alkylene group having 1 to 8 carbon atoms, such as methylene, ethyl, propyl, butyl, hexyl and octyl, is preferred. As Ar ₄ , an aromatic ring group having 6 to 18 carbon atoms is preferred, and a benzene ring group, a naphthyl ring group and a biphenyl ring group are more preferred. The repeating unit represented by the general formula (I) preferably has a hydroxystyrene structure. That is, Ar ₄ is preferably a benzene ring group.

As the repeating unit represented by the above general formula (I), the repeating unit represented by the following general formula (1) is preferred.

[Chemical formula 13]

In the general formula (1), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group. R represents a substituent. As the substituent represented by R, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group is preferred. In addition, when there are multiple R in the formula, they may be the same or different from each other, and multiple R may be bonded to each other to form a ring. a represents an integer from 1 to 3. b represents an integer from 0 to (5-a).

The following are examples of repeating units having an acid group. In the formula, a represents 1 or 2.

[Chemical formula 14]

[Chemical formula 15]

[Chemical formula 16]

In addition, among the above-mentioned repeating units, the repeating units specifically described below are preferred. In the formula, R represents a hydrogen atom or a methyl group, and a represents 2 or 3.

[Chemical formula 17]

[Chemical formula 18]

The content of the repeating unit having an acid group is preferably 5 mol% or more, more preferably 10 mol% or more, based on the total repeating units in the resin (A). The upper limit is not particularly limited, but is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less.

"Repeating units with fluorine atoms or iodine atoms" In addition to the above-mentioned "repeating units with acid-decomposable groups" and "repeating units with acid groups", the resin (A) may also have repeating units with fluorine atoms or iodine atoms. It is preferred that the "repeating units with fluorine atoms or iodine atoms" mentioned here are different from other types of repeating units belonging to Group A, such as the "repeating units with lactone groups, sultone groups or carbonate groups" and "repeating units with photoacid generating groups" described later.

As the repeating unit having a fluorine atom or an iodine atom, a repeating unit represented by formula (C) is preferred.

[Chemical formula 19]

_L5 represents a single bond or an ester group. _R9 represents a hydrogen atom, or an alkyl group which may have a fluorine atom or an iodine atom. _R10 represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group composed of these.

The following examples show repeating units having fluorine atoms or iodine atoms.

[Chemical formula 20]

The content of repeating units having fluorine atoms or iodine atoms is preferably 0 mol% or more, more preferably 5 mol% or more, and further preferably 10 mol% or more relative to the total repeating units in the resin (A). Moreover, as the upper limit, 50 mol% or less is preferably, 45 mol% or less is more preferably, and 40 mol% or less is further preferably. In addition, as described above, the repeating units having fluorine atoms or iodine atoms do not include "repeating units having acid-decomposable groups" and "repeating units having acid groups", so the content of repeating units having fluorine atoms or iodine atoms described above also represents the content of repeating units having fluorine atoms or iodine atoms other than "repeating units having acid-decomposable groups" and "repeating units having acid groups".

In the repeating units of the resin (A), the total content of the repeating units containing at least one of fluorine atoms and iodine atoms is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more relative to the total repeating units of the resin (A). The upper limit is not particularly limited, for example, it is 100 mol% or less. In addition, as repeating units containing at least one of fluorine atoms and iodine atoms, for example, repeating units having fluorine atoms or iodine atoms and having acid-decomposable groups, repeating units having fluorine atoms or iodine atoms and having acid groups, and repeating units having fluorine atoms or iodine atoms can be listed.

《Repeating units having lactone groups, sultone groups or carbonate groups》 The resin (A) may also have repeating units having at least one selected from lactone groups, sultone groups and carbonate groups (hereinafter collectively referred to as "repeating units having lactone groups, sultone groups or carbonate groups"). It is also preferred that the repeating units having lactone groups, sultone groups or carbonate groups do not have acid groups such as hexafluoropropanol groups.

As a lactone group or a sultone group, it is sufficient as long as it has a lactone structure or a sultone structure. The lactone structure or the sultone structure is preferably a 5-7-membered ring lactone structure or a 5-7-membered ring sultone structure. Among them, it is more preferable that another ring structure is fused to the 5-7-membered ring lactone structure in the form of a bicyclic structure or a spirocyclic structure, or another ring structure is fused to the 5-7-membered ring sultone structure in the form of a bicyclic structure or a spirocyclic structure. The resin (A) preferably has a repeating unit having a lactone group or a sultone group formed by removing one or more hydrogen atoms from a ring member atom of a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-21) or a sultone structure represented by any one of the following general formulas (SL1-1) to (SL1-3). In addition, the lactone group or the sultone group may also be directly bonded to the main chain. For example, the ring member atoms of the lactone group or the sultone group may also constitute the main chain of the resin (A).

[Chemical formula 21]

The lactone structure or sultone structure may also have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 1 to 8 carbon atoms, carboxyl groups, halogen atoms, hydroxyl groups, cyano groups, and acid-decomposable groups. n2 represents an integer of 0 to 4. When n2 is 2 or more, the plurality of Rb ₂ may be different, and the plurality of Rb ₂ may be bonded to each other to form a ring.

Examples of the repeating unit having a group having a lactone structure represented by any of the general formulae (LC1-1) to (LC1-21) or a sultone structure represented by any of the general formulae (SL1-1) to (SL1-3) include repeating units represented by the following general formula (AI).

[Chemical formula 22]

In the general formula (AI), _Rb0 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group of _Rb0 may have include a hydroxyl group and a halogen atom. Preferred halogen atom of _Rb0 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Preferably, _Rb0 is a hydrogen atom or a methyl group. Ab represents a divalent linking group having a single bond, an alkylene group, a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group combining these. Among them, a linking group represented by a single bond or _-Ab1 - _CO2- is preferred. Ab ₁ is a linear or branched alkylene group, or a monocyclic or polycyclic alkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornyl group. V represents a group formed by removing a hydrogen atom from a ring member atom of a lactone structure represented by any of the general formulae (LC1-1) to (LC1-21), or a group formed by removing a hydrogen atom from a ring member atom of a sultone structure represented by any of the general formulae (SL1-1) to (SL1-3).

When optical isomers exist in the repeating unit having a lactone group or a sultone group, any one of the optical isomers may be used. Moreover, one optical isomer may be used alone or a plurality of optical isomers may be used in combination. When one optical isomer is mainly used, its optical purity (ee) is preferably 90 or more, and more preferably 95 or more.

As the carbonate group, a cyclic carbonate group is preferred. As the repeating unit having a cyclic carbonate group, a repeating unit represented by the following general formula (A-1) is preferred.

[Chemical formula 23]

In the general formula (A- ¹ ), _RA1 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group). n represents an integer greater than or equal to 0. _RA2 represents a substituent. When n is greater than or equal to ² , a plurality ^of _RA2s may be the same or different. A represents a single bond or a divalent linking group. As the above-mentioned divalent linking group, a divalent linking group having an alkylene group, a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group formed by combining the above is preferred. Z represents an atomic group that forms a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

The following are examples of repeating units having a lactone group, a sultone group, or a carbonate group.

[Chemical formula 24]

[Chemical formula 25]

[Chemical formula 26]

The content of the repeating unit having a lactone group, a sultone group or a carbonate group is preferably 1 mol% or more, more preferably 5 mol% or more, based on the total repeating units in the resin (A). The upper limit is not particularly limited, but is preferably 65 mol% or less, more preferably 30 mol% or less, further preferably 25 mol% or less, and particularly preferably 20 mol% or less.

《Repeating unit having a photoacid generating group》 The resin (A) may also have a repeating unit having a group that generates an acid by irradiation with actinic rays or radiation (hereinafter also referred to as a "photoacid generating group") as a repeating unit other than the above. In this case, the repeating unit having the photoacid generating group can be considered to be a compound that generates an acid by irradiation with actinic rays or radiation described later (also referred to as a "photoacid generator"). As such a repeating unit, for example, a repeating unit represented by the following general formula (4) can be cited.

[Chemical formula 27]

R ⁴¹ represents a hydrogen atom or a methyl group. L ⁴¹ represents a single bond or a divalent linking group. L ⁴² represents a divalent linking group. R ⁴⁰ represents a structural site that generates an acid in the side chain by decomposition due to irradiation with actinic rays or radiation.

The following are examples of repeating units having a photoacid generating group.

[Chemical formula 28]

[Chemical formula 29]

Examples of the repeating unit represented by the general formula (4) include the repeating units described in paragraphs [0094] to [0105] of Japanese Patent Application Laid-Open No. 2014-041327.

The content of the repeating unit having a photoacid generating group is preferably 1 mol% or more, more preferably 5 mol% or more, based on the total repeating units in the resin (A). The upper limit thereof is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less.

《Repeating units represented by general formula (V-1) or the following general formula (V-2)》 The resin (A) may also have repeating units represented by the following general formula (V-1) or the following general formula (V-2). It is preferred that the repeating units represented by the following general formula (V-1) and the following general formula (V-2) are different from the above-mentioned repeating units.

[Chemical formula 30]

In the formula, _R6 and _R7 independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms) or a carboxyl group. As the alkyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferred. _n3 represents an integer of 0 to 6. _n4 represents an integer of 0 to 4. _X4 represents a methylene group, an oxygen atom or a sulfur atom. The following examples show the repeating units represented by the general formula (V-1) or (V-2).

[Chemical formula 31]

《Repeating units for reducing the mobility of the main chain》 From the perspective of being able to suppress excessive diffusion of the generated acid or pattern collapse during development, the glass transition temperature (Tg) of the resin (A) is preferably higher. Tg greater than 90°C is preferred, greater than 100°C is more preferred, greater than 110°C is further preferred, and greater than 125°C is particularly preferred. In addition, excessively high Tg will lead to a decrease in the dissolution rate in the developer, so Tg is preferably below 400°C, and more preferably below 350°C. In addition, in this specification, the glass transition temperature (Tg) of polymers such as resin (A) is calculated by the following method. First, the Tg of the homopolymer including only each repeating unit contained in the polymer is calculated separately by the Bicerano method. Hereinafter, the calculated Tg is referred to as "Tg of repeating unit". Next, the mass ratio (%) of each repeating unit relative to the total repeating units in the polymer is calculated. Next, the Tg at each mass ratio is calculated using Fox's formula (described in Materials Letters 62 (2008) 3152, etc.), and these are added together to be the Tg (°C) of the polymer. The Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993), etc. In addition, the Tg calculation based on the Bicerano method can be performed using the polymer property calculation software MDL Polymer (MDL Information Systems, Inc.).

In order to increase the Tg of the resin (A) (preferably to set the Tg to more than 90°C), it is preferable to reduce the mobility of the main chain of the resin (A). The following methods (a) to (e) can be listed as methods for reducing the mobility of the main chain of the resin (A). (a) Introducing a large-volume substituent into the main chain (b) Introducing multiple substituents into the main chain (c) Introducing a substituent that causes interaction between resins (A) near the main chain (d) Main chain forming a ring structure (e) Connecting a ring structure to the main chain In addition, it is preferable that the resin (A) has a repeating unit whose homopolymer Tg is 130°C or more. In addition, the type of repeating unit having a homopolymer Tg of 130°C or higher is not particularly limited, as long as it is a repeating unit having a homopolymer Tg of 130°C or higher calculated by the Bicerano method. In addition, the type of functional groups in the repeating units represented by the formulas (A) to (E) described below corresponds to the repeating unit having a homopolymer Tg of 130°C or higher.

(Repeating unit represented by formula (A)) As an example of a specific implementation of the above (a), there can be cited a method of introducing a repeating unit represented by formula (A) into a resin (A).

[Chemical formula 32]

In formula (A), _RA represents a group having a polycyclic structure. _Rx represents a hydrogen atom, a methyl group or an ethyl group. A group having a polycyclic structure is a group having a plurality of ring structures, and the plurality of ring structures may be fused or not. As specific examples of the repeating unit represented by formula (A), the following repeating units can be listed.

[Chemical formula 33]

[Chemical formula 34]

[Chemical formula 35]

In the above formula, R represents a hydrogen atom, a methyl group or an ethyl group. Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR''' or -COOR''': R''' is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the above alkyl group, the above cycloalkyl group, the above aryl group, the above aralkyl group and the above alkenyl group may also have substituents, respectively. Furthermore, the hydrogen atom bonded to the carbon atom in the group represented by Ra may be substituted by a fluorine atom or an iodine atom. Furthermore, R' and R'' independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amine group, a halogen atom, an ester group (-OCOR''' or -COOR''': R''' is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the above-mentioned alkyl group, the above-mentioned cycloalkyl group, the above-mentioned aryl group, the above-mentioned aralkyl group and the above-mentioned alkenyl group may also have a substituent. Furthermore, the hydrogen atom bonded to the carbon atom in the group represented by R' and R'' may be substituted by a fluorine atom or an iodine atom. L represents a single bond or a divalent linking group. Examples of the divalent linking group include -COO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, an alkylene group, a cycloalkylene group, an alkenylene group and a linking group having a plurality of these groups connected thereto. m and n each independently represent an integer greater than 0. The upper limits of m and n are not particularly limited, but are often less than 2, and more often less than 1.

(Repeating unit represented by formula (B)) As an example of a specific implementation method of the above (b), a method of introducing a repeating unit represented by formula (B) into resin (A) can be cited.

[Chemical formula 36]

In formula (B), R _b1 to R _b4 each independently represent a hydrogen atom or an organic group, and at least two of R _b1 to R _b4 represent an organic group. Furthermore, when at least one of the organic groups is a group having a cyclic structure directly connected to the main chain in the repeating unit, the types of the other organic groups are not particularly limited. Furthermore, when any of the organic groups is not a group having a cyclic structure directly connected to the main chain in the repeating unit, at least two of the organic groups are substituents having 3 or more constituent atoms other than hydrogen atoms.

As specific examples of the repeating unit represented by formula (B), the following repeating units can be cited.

[Chemical formula 37]

In the above formula, R independently represents a hydrogen atom or an organic group. As the organic group, there can be listed organic groups such as alkyl, cycloalkyl, aryl, aralkyl and alkenyl groups which may also have a substituent. R' independently represents an alkyl, cycloalkyl, aryl, aralkyl, alkenyl, hydroxyl, alkoxy, acyloxy, cyano, nitro, amino, halogen atom, ester group (-OCOR'' or -COOR'': R'' is an alkyl or fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the above alkyl, the above cycloalkyl, the above aryl, the above aralkyl and the above alkenyl groups may also have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R' may also be substituted by a fluorine atom or an iodine atom. m represents an integer greater than 0. There is no particular limit on the upper limit of m, and most of them are 2 or less, and more often 1 or less.

(Repeating unit represented by formula (C)) As an example of a specific implementation of the above (c), there can be cited a method of introducing a repeating unit represented by formula (C) into the resin (A).

[Chemical formula 38]

In formula (C), _Rc1 to _Rc4 each independently represent a hydrogen atom or an organic group, and at least one of _Rc1 to _Rc4 is a group of hydrogen atoms having hydrogen bonding properties within 3 atoms from the main chain carbon. Among them, hydrogen atoms having hydrogen bonding properties within 2 atoms (closer to the main chain side) are preferred in order to cause interaction between the main chains of the resin (A).

As specific examples of the repeating unit represented by formula (C), the following repeating units can be cited.

[Chemical formula 39]

In the above formula, R represents an organic group. As the organic group, alkyl, cycloalkyl, aryl, aralkyl, alkenyl and ester groups (-OCOR or -COOR: R is an alkyl or fluorinated alkyl group having 1 to 20 carbon atoms) which may also have a substituent can be listed. R' represents a hydrogen atom or an organic group. As the organic group, organic groups such as alkyl, cycloalkyl, aryl, aralkyl and alkenyl can be listed. In addition, the hydrogen atom in the organic group can also be substituted by a fluorine atom or an iodine atom.

(Repeating unit represented by formula (D)) As an example of a specific implementation of the above (d), a method of introducing a repeating unit represented by formula (D) into resin (A) can be cited.

[Chemical formula 40]

In formula (D), "cylic" represents a group having a cyclic structure as the main chain. The number of atoms constituting the ring is not particularly limited.

As specific examples of the repeating unit represented by formula (D), the following repeating units can be cited.

[Chemical formula 41]

In the above formula, R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amine group, a halogen atom, an ester group (-OCOR'' or -COOR'': R'' is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the above alkyl group, the above cycloalkyl group, the above aryl group, the above aralkyl group and the above alkenyl group may also have substituents. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R may also be substituted by a fluorine atom or an iodine atom. In the above formula, R' independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amine group, a halogen atom, an ester group (-OCOR'' or -COOR'': R'' is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the above alkyl group, the above cycloalkyl group, the above aryl group, the above aralkyl group and the above alkenyl group may also have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R' may also be substituted by a fluorine atom or an iodine atom. m represents an integer greater than 0. There is no particular upper limit on m, and most of them are 2 or less, and more often 1 or less.

(Repeating unit represented by formula (E)) As an example of a specific implementation of the above (e), a method of introducing a repeating unit represented by formula (E) into the resin (A) can be cited.

[Chemical formula 42]

In formula (E), Re independently represents a hydrogen atom or an organic group. Examples of the organic group include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups, which may also have substituents. "Cylic" is a cyclic group containing carbon atoms in the main chain. There is no particular limitation on the number of atoms contained in the cyclic group.

As specific examples of the repeating unit represented by formula (E), the following repeating units can be cited.

[Chemical formula 43]

[Chemical formula 44]

In the above formula, R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amine group, a halogen atom, an ester group (-OCOR'' or -COOR'': R'' is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the above alkyl group, the above cycloalkyl group, the above aryl group, the above aralkyl group and the above alkenyl group may also have substituents. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R may also be substituted by a fluorine atom or an iodine atom. R' independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR'' or -COOR'': R'' is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the above-mentioned alkyl group, the above-mentioned cycloalkyl group, the above-mentioned aryl group, the above-mentioned aralkyl group and the above-mentioned alkenyl group may also have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R' may also be substituted by a fluorine atom or an iodine atom. m represents an integer greater than 0. The upper limit of m is not particularly limited, and is mostly 2 or less, and more often 1 or less. In addition, in formula (E-2), formula (E-4), formula (E-6) and formula (E-8), two Rs may also be bonded to each other to form a ring.

The content of the repeating unit represented by formula (E) is preferably 5 mol% or more, more preferably 10 mol% or more, based on the total repeating units in the resin (A). The upper limit is preferably 60 mol% or less, more preferably 55 mol% or less.

"Repeating units having at least one group selected from lactone, sultone, carbonate, hydroxyl, cyano and alkali-soluble groups" Resin (A) may also have repeating units having at least one group selected from lactone, sultone, carbonate, hydroxyl, cyano and alkali-soluble groups. Repeating units having lactone, sultone or carbonate groups in resin (A) may include the repeating units described in the above "Repeating units having lactone, sultone or carbonate groups". The preferred content is also as described in the above "Repeating units having lactone, sultone or carbonate groups".

The resin (A) may also have a repeating unit having a hydroxyl group or a cyano group. This improves substrate adhesion and developer affinity. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. The repeating unit having a hydroxyl group or a cyano group is preferably one that does not have an acid-decomposable group. As repeating units having a hydroxyl group or a cyano group, repeating units represented by the following general formulas (AIIa) to (AIId) can be cited.

[Chemical formula 45]

In general formulae (AIIa) to (AIId), R _1c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. R _2c to R _4c each independently represent a hydrogen atom, a hydroxyl group or a cyano group. At least one of R _2c to R _4c represents a hydroxyl group or a cyano group. Preferably, one or two of R _2c to R _4c are hydroxyl groups, and the remainder are hydrogen atoms. More preferably, two of R _2c to R _4c are hydroxyl groups, and the remainder are hydrogen atoms.

The content of the repeating unit having a hydroxyl group or a cyano group is preferably 5 mol% or more, more preferably 10 mol% or more, and the upper limit thereof is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, relative to the total repeating units in the resin (A).

Specific examples of repeating units having a hydroxyl group or a cyano group are listed below, but the present invention is not limited thereto.

[Chemical formula 46]

The resin (A) may also have a repeating unit having an alkali-soluble group. As the alkali-soluble group, there can be listed a carboxyl group, a sulfonylamide group, a sulfonyl imide group, a disulfonyl imide group, and an aliphatic alcohol substituted with an electron-withdrawing group at the α position (e.g., a hexafluoroisopropanol group), and a carboxyl group is preferred. The resin (A) has an increased resolution when used for contact hole purposes by including a repeating unit having an alkali-soluble group. As repeating units having an alkali-soluble group, repeating units based on acrylic acid and methacrylic acid, which are directly bonded to the main chain of the resin, or repeating units having an alkali-soluble group bonded to the main chain of the resin via a linking group, can be cited. In addition, the linking group may also have a monocyclic or polycyclic cyclic hydrocarbon structure. As repeating units having an alkali-soluble group, repeating units based on acrylic acid or methacrylic acid are preferred.

The content of the repeating unit having an alkali-soluble group is preferably 0 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, with respect to the total repeating units in the resin (A). The upper limit thereof is preferably 20 mol% or less, more preferably 15 mol% or less, and even more preferably 10 mol% or less.

Specific examples of the repeating unit having an alkali-soluble group are shown below, but the present invention is not limited thereto. In the specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

[Chemical formula 47]

As the repeating unit having at least one group selected from the group consisting of a lactone group, a hydroxyl group, a cyano group and an alkali-soluble group, a repeating unit having at least two groups selected from the group consisting of a lactone group, a hydroxyl group, a cyano group and an alkali-soluble group is preferred, a repeating unit having a cyano group and a lactone group is more preferred, and a repeating unit having a structure in which a cyano group is substituted on the lactone structure represented by the general formula (LC1-4) is further preferred.

《Repeating units having an alicyclic hydrocarbon structure and not showing acid decomposition》 The resin (A) may also have an alicyclic hydrocarbon structure and a repeating unit that is not showing acid decomposition. This can reduce the dissolution of low molecular weight components from the resist film into the immersion liquid during immersion exposure. Examples of such repeating units include repeating units derived from 1-adamantyl (meth)acrylate, diamond alkyl (meth)acrylate, tricyclodecyl (meth)acrylate, or cyclohexyl (meth)acrylate.

"Repeating units not having either a hydroxyl group or a cyano group and represented by the general formula (III)" The resin (A) may also have repeating units not having either a hydroxyl group or a cyano group and represented by the general formula (III).

[Chemical formula 48]

In the general formula (III), R ₅ represents a alkyl group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group. Ra represents a hydrogen atom, an alkyl group, or a -CH ₂ -O-Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group, or an acyl group.

The cyclic structure possessed by R ₅ includes a monocyclic alkyl group and a polycyclic alkyl group. Examples of the monocyclic alkyl group include a cycloalkyl group having 3 to 12 carbon atoms (more preferably 3 to 7 carbon atoms) or a cycloalkenyl group having 3 to 12 carbon atoms.

Examples of the polycyclic alkyl group include ring-aggregated alkyl groups and cross-linked cyclic alkyl groups. Examples of the cross-linked cyclic alkyl group include bicyclic alkyl groups, tricyclic alkyl groups, and tetracyclic alkyl groups. Furthermore, cross-linked cyclic alkyl groups include condensed rings in which a plurality of 5- to 8-membered cycloalkane alkyl rings are condensed. As the cross-linked cyclic alkyl group, a norbornyl group, an adamantyl group, a bicyclooctyl group, or a tricyclo[5,2,1,0 ^{2 , 6} ]decyl group is preferred, and a norbornyl group or an adamantyl group is more preferred.

The alicyclic alkyl group may also have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, and an amino group protected by a protecting group. As the halogen atom, a bromine atom, a chlorine atom, or a fluorine atom is preferred. As the alkyl group, a methyl group, an ethyl group, a butyl group, or a tert-butyl group is preferred. The above-mentioned alkyl group may also have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, or an amino group protected by a protecting group.

As the protecting group, for example, an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group can be listed. As the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferred. As the substituted methyl group, a methoxymethyl group, a methoxythiomethyl group, a benzyloxymethyl group, a tert-butoxymethyl group, or a 2-methoxyethoxymethyl group is preferred. As the substituted ethyl group, a 1-ethoxyethyl group or a 1-methyl-1-methoxyethyl group is preferred. As the acyl group, an aliphatic acyl group having 1 to 6 carbon atoms, such as a methyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pentyl group, and a trimethylacetyl group is preferred. As the alkoxycarbonyl group, an alkoxycarbonyl group having 1 to 4 carbon atoms is preferred.

The content of the repeating unit represented by the general formula (III) which does not have any hydroxyl group or cyano group is preferably 0 to 40 mol %, more preferably 0 to 20 mol % relative to the total repeating units in the resin (A). Specific examples of the repeating unit represented by the general formula (III) are listed below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH or CF ₃ .

[Chemical formula 49]

《Other repeating units》 In addition, the resin (A) may also have repeating units other than the above-mentioned repeating units. For example, the resin (A) may also have repeating units selected from repeating units having an oxythiocarbonyl ring group, repeating units having an oxazolinone ring group, repeating units having a dioxazolinone ring group, and repeating units having a hydantoin ring group. The following is an example of such repeating units.

[Chemical formula 50]

In addition to the above-mentioned repetitive structural units, the resin (A) may also have various repetitive structural units for the purpose of adjusting the etching resistance, compatibility with standard developer, substrate adhesion, resist profile, resolution, heat resistance and sensitivity.

It is also preferred that the resin (A) has all repeating units composed of (meth)acrylate repeating units (especially when the composition is used for ArF applications). In this case, any of a resin having all repeating units composed of methacrylate repeating units, a resin having all repeating units composed of acrylate repeating units, and a resin having all repeating units composed of methacrylate repeating units and acrylate repeating units can be used, and it is preferred that the acrylate repeating units account for 50 mol% or less of the total repeating units.

The resin (A) can be synthesized by a conventional method (e.g., free radical polymerization). As a polystyrene conversion value by GPC method, the weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 5,000 to 15,000. By setting the weight average molecular weight of the resin (A) to 1,000 to 200,000, the deterioration of heat resistance and etching resistance can be further suppressed. In addition, the deterioration of developing property and the deterioration of film forming property due to increased viscosity can be further suppressed. The dispersion degree (molecular weight distribution) of the resin (A) is usually 1 to 5, 1 to 3 is preferred, 1.2 to 3.0 is more preferred, and 1.2 to 2.0 is further preferred. The smaller the dispersion degree, the better the resolution and resist shape, and the smoother the sidewall of the resist pattern and the better the roughness.

In the inhibitor composition, the content of the resin (A) is preferably 50 to 99.9 mass % relative to the total solid content of the composition, and more preferably 60 to 99.0 mass %. In addition, the solid component refers to the components other than the solvent in the composition, and as long as it is a component other than the solvent, it can be either a liquid component or a solid component. In addition, the resin (A) can be used alone or in combination of multiple types.

>Compounds that generate acid by actinic rays or radiation (photoacid generator)> The resist composition preferably contains a compound that generates acid by actinic rays or radiation (hereinafter, also referred to as "photoacid generator <PAG: Photo Acid Generator>"). The photoacid generator may be in the form of a low molecular weight compound or in the form of being incorporated into a part of a polymer. In addition, the form of a low molecular weight compound and the form of being incorporated into a part of a polymer may be used together. When the photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less. When the photoacid generator is in the form of being incorporated into a part of a polymer, it may be incorporated into a part of the resin (A) or into a resin different from the resin (A). In the present invention, the photoacid generator is preferably in the form of a low molecular weight compound. The photoacid generator is not particularly limited as long as it is a known one, but the actinic ray or radiation is preferably a compound that generates an organic acid such as sulfonic acid, bis(alkylsulfonyl)imide or tri(alkylsulfonyl)methyl by irradiation with electron beam or extreme ultraviolet light. More preferably, the compound can be represented by the following general formula (ZI), (ZII) and (ZIII).

[Chemical formula 51]

In the above general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group. The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is usually 1 to 30, preferably 1 to 20. In addition, two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group in the ring. As the group formed by two of R ₂₀₁ to R ₂₀₃ being bonded, an alkyl group (for example, a butyl group, a pentenyl group) can be listed. Z ^- represents a non-nucleophilic anion (an anion having a significantly low ability to cause a nucleophilic reaction).

Examples of the non-nucleophilic anion include sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, camphorsulfonic acid anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, aralkyl carboxylic acid anions, etc.), sulfonyl imide anions, bis(alkylsulfonyl)imide anions, tris(alkylsulfonyl)methide anions, and the like.

The aliphatic part in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms.

The aromatic group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group having 6 to 14 carbon atoms, for example, phenyl, tolyl, naphthyl and the like can be mentioned.

The alkyl, cycloalkyl and aryl groups listed above may also have a substituent. Specific examples thereof include a nitro group, a halogen atom such as a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 1 5), alkylsulfonyl (preferably having 1 to 15 carbon atoms), alkyliminosulfonyl (preferably having 1 to 15 carbon atoms), aryloxysulfonyl (preferably having 6 to 20 carbon atoms), alkylaryloxysulfonyl (preferably having 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl (preferably having 10 to 20 carbon atoms), alkoxyalkoxy (preferably having 5 to 20 carbon atoms), cycloalkylalkoxyalkoxy (preferably having 8 to 20 carbon atoms), etc. Regarding the aryl and ring structures possessed by each group, an alkyl group (preferably having 1 to 15 carbon atoms) can also be listed as a substituent.

The aralkyl group in the aralkylcarboxylic acid anion is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and naphthylbutyl.

As the sulfonylimide anion, for example, saccharin anion can be mentioned.

The alkyl group in the bis(alkylsulfonyl)imide anion and the tri(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. As substituents of the alkyl groups, halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkoxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, etc. can be listed, and fluorine atoms or alkyl groups substituted with fluorine atoms are preferred. In addition, the alkyl groups in the bis(alkylsulfonyl)imide anion can also bond with each other to form a ring structure. Thereby, the acid strength is increased.

As other non-affinity anions, for example, phosphorus fluoride (eg, PF ₆ ^- ), boron fluoride (eg, BF ₄ ^- ), antimony fluoride (eg, SbF ₆ ^- ), and the like can be listed.

As the non-affinity anion, an aliphatic sulfonic acid anion in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion substituted with a fluorine atom or a group having a fluorine atom, a bis(alkylsulfonyl)imide anion in which the alkyl group is substituted with a fluorine atom, and a tris(alkylsulfonyl)methyl anion in which the alkyl group is substituted with a fluorine atom are preferred. As the non-affinity anion, a perfluoroaliphatic sulfonic acid anion (more preferably having 4 to 8 carbon atoms), a benzenesulfonic acid anion having a fluorine atom, and more preferably a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, a pentafluorobenzenesulfonic acid anion, and a 3,5-bis(trifluoromethyl)benzenesulfonic acid anion are more preferred.

From the perspective of acid strength, in order to improve sensitivity, it is best if the pKa of the generated acid is below -1.

In addition, as a preferred aspect of the non-affinity anion, an anion represented by the following general formula (AN1) can also be cited.

[Chemical formula 52]

In the formula, Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are plural R ¹ and R ² , they may be the same or different. L represents a divalent linking group, and when there are plural L, they may be the same or different. A represents a cyclic organic group. x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

The general formula (AN1) is further described in detail. The alkyl group in the alkyl group substituted by a fluorine atom as Xf is preferably a group having 1 to 10 carbon atoms, and more preferably a group having 1 to 4 carbon atoms. Furthermore, the alkyl group substituted by a fluorine atom as Xf is preferably a perfluoroalkyl group. As Xf, a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms is preferred. Specific examples of Xf include fluorine atom, _CF3 , _{C2F5 , C3F7 , C4F9 , CH2CF3 , CH2CH2CF3 , CH2C2F5 , CH2CH2C2F5 , CH2C3F7 , CH2CH2C3F7 , CH2C4F9 , and CH2CH2C4F9 .} Among them _, fluorine _{atom and CF3 are preferred .} In particular, _it is preferred that _{two Xf} are fluorine atoms.

The alkyl group represented by R ¹ and R ² may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms, and more preferably is a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent for ^R1 and ^R2 include _CF3 , _C2F5 , _{C3F7 , C4F9 , C5F11 , C6F13 , C7F15 , C8F17 , CH2CF3 , CH2CH2CF3 , CH2C2F5 , CH2CH2C2F5 , CH2C3F7 , CH2CH2C3F7 , CH2C4F9 , and CH2CH2C4F9 ,} among _{which CF3} ^is _{preferred . R1 and R2} are _{preferably a fluorine} atom _{or CF3} ^.

x is preferably 1 to 10, more preferably 1 to 5. y is preferably 0 to 4, more preferably 0. z is preferably 0 to 5, more preferably 0 to 3. The divalent linking group as L is not particularly limited, and includes -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene, cycloalkylene, alkenylene, or a plurality of these linking groups, and a linking group having a total carbon number of 12 or less is preferred. Among them, -COO-, -OCO-, -CO-, -O- are preferred, and -COO- and -OCO- are more preferred.

In the general formula (AN1), preferred examples of the combination of partial structures other than A include ^SO3 -- _CF2 - _CH2 -OCO-, SO3 ^-- _CF2 -CHF- _CH2 -OCO-, SO3 ^-- CF2 _- COO-, SO3 ^-- _CF2 - _{CF2 -} CH2-, and ^SO3-- _CF2 -CH( _CF3 )-OCO-.

The cyclic organic group A is not particularly limited as long as it has a cyclic structure, and examples thereof include alicyclic groups, aryl groups, heterocyclic groups (including not only aromatic groups but also non-aromatic groups), etc. The alicyclic group may be monocyclic or polycyclic, and monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl, and polycyclic cycloalkyl groups such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl are preferred. Among them, from the viewpoint of being able to suppress diffusion in the film in the post-exposure heating step and improve MEEF (mask error enhancement factor), alicyclic groups with a large structure having a carbon number of 7 or more, such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl, are preferred. As the aromatic group, benzene ring, naphthalene ring, phenanthrene ring, and anthracene ring can be listed. As the heterocyclic group, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring can be listed. Among them, furan ring, thiophene ring, and pyridine ring are preferred.

Furthermore, as the cyclic organic group, a lactone structure can also be listed, and as specific examples, lactone structures represented by the following general formulas (LC1-1) to (LC1-17) can be listed.

[Chemical formula 53]

The above-mentioned cyclic organic group may also have a substituent. Examples of the above-mentioned substituent include alkyl groups (straight chain, branched chain and cyclic groups may be used, preferably having 1 to 12 carbon atoms), cycloalkyl groups (monocyclic, polycyclic and spirocyclic groups may be used, preferably having 3 to 20 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), hydroxyl groups, alkoxyl groups, ester groups, amide groups, carbamate groups, urea groups, sulfide groups, sulfonamide groups, sulfonate groups and the like. In addition, the carbon (carbon that contributes to the formation of the ring) constituting the cyclic organic group may be a carbonyl carbon. In addition, the above-mentioned substituents are equivalent to Rb ₂ in the above-mentioned (LC1-1) to (LC1-17). In the above-mentioned (LC1-1) to (LC1-17), n2 represents an integer of 0 to 4. When n2 is 2 or more, the multiple _Rb2s may be the same or different, and the multiple _Rb2s may be bonded to each other to form a ring.

In the general formula (ZI), the organic groups of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include aryl groups, alkyl groups, cycloalkyl groups and the like. It is preferred that at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is an aryl group, and it is more preferred that all three of them are aryl groups. The aryl group may be a phenyl group, a naphthyl group, or a heteroaryl group such as an indole residue or a pyrrole residue. The alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ may preferably include a linear or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. The alkyl group may more preferably include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and the like. As the cycloalkyl group, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc. can be preferably listed. These groups may further have substituents. As substituents that may be further possessed, nitro, halogen atoms such as fluorine atoms, carboxyl, hydroxyl, amino, cyano, alkoxy (preferably carbon number 1-15), cycloalkyl (preferably carbon number 3-15), aryl (preferably carbon number 6-14), alkoxycarbonyl (preferably carbon number 2-7), acyl (preferably carbon number 2-12), alkoxycarbonyloxy (preferably carbon number 2-7), etc. can be listed, but it is not limited to them.

Next, general formulae (ZII) and (ZIII) are described. In general formulae (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ independently represent an aryl group, an alkyl group, or a cycloalkyl group. As the aryl group of R ₂₀₄ to R ₂₀₇ , phenyl and naphthyl are preferred, and phenyl is further preferred. The aryl group of R ₂₀₄ to R ₂₀₇ may also be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, and the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, and the like. As the alkyl group and cycloalkyl group for R ₂₀₄ to R ₂₀₇ , preferably there can be mentioned a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl) and a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl, cyclohexyl, norbornyl).

The aryl group, alkyl group and cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ may have a substituent. Examples of the substituent that the aryl group, alkyl group and cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ may have include an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 15 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group and a phenylthio group.

In the general formula (ZII), ^Z- represents a non-nucleophilic anion. Specifically, it is the same as described as ^Z- in the general formula (ZI), and the preferred embodiment is also the same.

Specific examples of general formulae (ZI) to (ZIII) are shown below, but are not limited thereto.

[Chemical formula 54]

In the present invention, from the viewpoint of suppressing the diffusion of the acid generated during exposure to the non-exposed part and optimizing the resolution, the photoacid generator is a compound that generates an acid (preferably a sulfonic acid) with a volume of 130Å ³ or more by irradiation with an electron beam or extreme ultraviolet light, a compound that generates an acid (preferably a sulfonic acid) with a volume of 190Å ³ or more is more preferred, a compound that generates an acid (preferably a sulfonic acid) with a volume of 270Å ³ or more is more preferred, and a compound that generates an acid (preferably a sulfonic acid) with a volume of 400Å ³ or more is particularly preferred. Among them, from the viewpoint of sensitivity and solubility in coating solvents, the above-mentioned volume is preferably 2000Å ³ or less, and more preferably 1500Å ³ or less. The above volume values are obtained using "WinMOPAC" manufactured by FUJITSU LIMITED. That is, first, the chemical structure of the acid in each example is input, and then the structure is used as the initial structure, and the most stable stereo configuration of each acid is determined by molecular force field calculation using the MM3 method. Thereafter, the molecular orbital calculation using the PM3 method is performed on the most stable stereo configuration, thereby being able to calculate the "accessible volume" of each acid. In addition, 1Å represents 0.1nm. In the present invention, a photoacid generator that generates the following acid by irradiation with actinic rays or radiation is preferred. In addition, the calculated value of the volume (unit Å ³ ) is marked for some examples. In addition, the calculated value obtained here is the volume value of the acid with a proton bonded to the anion part.

[Chemical formula 55]

[Chemical formula 56]

[Chemical formula 57]

As the photoacid generator, paragraphs <0368> to <0377> of Japanese Patent Publication No. 2014-041328 and paragraphs <0240> to <0262> of Japanese Patent Publication No. 2013-228681 (corresponding to <0339> of the specification of U.S. Patent Application Publication No. 2015/0004533) can be cited, and the contents are incorporated into this specification. In addition, as preferred specific examples, the following compounds can be listed, but are not limited to them.

[Chemical formula 58]

[Chemical formula 59]

[Chemical formula 60]

[Chemical formula 61]

The photoacid generator can be used alone or in combination of two or more. The content of the photoacid generator in the resist composition is preferably 0.1 to 50% by mass, more preferably 5 to 50% by mass, and even more preferably 8 to 40% by mass, based on the total solid content of the composition. In particular, when performing electron beam or extreme ultraviolet exposure, in order to achieve both high sensitivity and high resolution, the content of the photoacid generator is preferably higher. From the above viewpoints, 10 to 40% by mass is preferred, and 10 to 35% by mass is even more preferred.

<Solvent> When dissolving the above components to prepare the inhibitor composition, a solvent can be used. Examples of the solvent that can be used include organic solvents such as alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic lactone having 4 to 10 carbon atoms, monoketone compound having 4 to 10 carbon atoms that may contain a ring, alkylene carbonate, alkyl alkoxy acetate, and alkyl pyruvate.

As the alkylene glycol monoalkyl ether carboxylate, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate can be preferably listed. As the alkylene glycol monoalkyl ether, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether can be preferably listed.

As the alkyl lactate, for example, methyl lactate, ethyl lactate, propyl lactate, and butyl lactate are preferably listed. As the alkyl alkoxypropionate, for example, ethyl 3-ethoxypropionate, 3-methoxypropionate, 3-ethoxymethylpropionate, and ethyl 3-methoxypropionate are preferably listed.

Preferred examples of the cyclic lactone having 4 to 10 carbon atoms include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-octanoic acid lactone, and α-hydroxy-γ-butyrolactone.

As the monoketone compound having 4 to 10 carbon atoms and which may contain a ring, for example, preferably 2-butanone, 3-methylbutanone, tert-butylethylketone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6 ... Methyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcycloheptanone.

As the alkyl carbonate, for example, propylene carbonate, vinyl carbonate, ethyl carbonate, and butyl carbonate can be preferably listed. As the alkyl alkoxy acetate, for example, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-2-propyl acetate can be preferably listed. As the alkyl pyruvate, for example, methyl pyruvate, ethyl pyruvate, and propyl pyruvate can be preferably listed. As the solvent that can be preferably used, a solvent having a boiling point of 130° C. or more at normal temperature and pressure can be listed. Specifically, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate, and propylene carbonate can be listed. In the present invention, the above solvents can be used alone or in combination of two or more.

In the present invention, a mixed solvent obtained by mixing a solvent containing a hydroxyl group in its structure with a solvent not containing a hydroxyl group can also be used as an organic solvent. As the solvent containing a hydroxyl group, for example, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, etc. can be listed, among which propylene glycol monomethyl ether and ethyl lactate are particularly preferred. As the solvent not containing a hydroxyl group, for example, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, etc. can be listed. Among them, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, and 2-heptanone are the best. As the mixing ratio (mass ratio) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, it is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, and further preferably 20/80 to 60/40. A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly good in terms of coating uniformity.

The solvent is preferably a mixed solvent of two or more solvents including propylene glycol monomethyl ether acetate, and the combination of γ-butyrolactone and butyl acetate is particularly preferred.

As the solvent, for example, the solvents described in paragraphs 0013 to 0029 of Japanese Patent Application Laid-Open No. 2014-219664 can be used.

<Alkaline compound> In order to reduce the performance change over time from exposure to heating, the resist composition preferably contains (E) an alkaline compound. As the alkaline compound, a compound having a structure represented by the following formulas (A1) to (E1) is preferred.

[Chemical formula 62]

In the general formulae (A1) and (E1), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and represent a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 20 carbon atoms). Here, R ²⁰¹ and R ²⁰² may also be bonded to each other to form a ring.

As for the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferred. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , and R ²⁰⁶ may be the same or different and represent an alkyl group having 1 to 20 carbon atoms. It is more preferred that the alkyl group in the general formulas (A1) and (E1) is unsubstituted.

Preferred compounds include, in addition to guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperidine, aminopyrrolidine, aminoalkylpyrrolidine, and piperidine, compounds having an imidazole structure, a diazepine bicyclic structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, or a pyridine structure, alkylamine derivatives having a hydroxyl group and/or an ether bond, and aniline derivatives having a hydroxyl group and/or an ether bond.

Examples of the compound including an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, etc. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, 1,8-diazabicyclo[5,4,0]undec-7-ene, etc. Examples of compounds having an onium hydroxide structure include triarylcosium hydroxide, benzylmethylcosium hydroxide, and cosium hydroxide having a 2-oxoalkyl group, specifically triphenylcosium hydroxide, tri(tert-butylphenyl)cosium hydroxide, bis(tert-butylphenyl)iodonium hydroxide, benzylmethylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. Examples of compounds having an onium carboxylate structure include compounds having an onium hydroxide structure in which the anion portion is a carboxylate ester, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of compounds having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of aniline compounds include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of alkylamine derivatives having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine, and tris(methoxyethoxyethyl)amine. Examples of aniline derivatives having a hydroxyl group and/or an ether bond include N,N-bis(hydroxyethyl)aniline.

Preferred alkaline compounds include amine compounds having a phenoxy group and ammonium salt compounds having a phenoxy group.

The amine compound can be a primary, secondary, or tertiary amine compound, and an amine compound having at least one alkyl group bonded to a nitrogen atom is preferred. It is more preferred that the amine compound be a tertiary amine compound. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the amine compound may be a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 12 carbon atoms) bonded to the nitrogen atom in addition to the alkyl group. In addition, the amine compound preferably has an oxygen atom in the alkyl chain to form an oxyalkylene group. The number of oxyalkylene groups in the molecule is 1 or more, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, oxyethylene (-CH ₂ CH ₂ O-) or oxypropylene (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) is preferred, and oxyethylene is more preferred.

The ammonium salt compound can be primary, secondary, tertiary, or quaternary ammonium salt compounds, and ammonium salt compounds in which at least one alkyl group is bonded to a nitrogen atom are preferred. In addition to the alkyl group, a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 12 carbon atoms) may be bonded to the nitrogen atom as long as the ammonium salt compound has at least one alkyl group (preferably having 1 to 20 carbon atoms) bonded to the nitrogen atom. The ammonium salt compound preferably has an oxygen atom in the alkyl chain to form an oxyalkylene group. The number of oxyalkylene groups in the molecule is 1 or more, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, oxyethylene ( _-CH2CH2O- ) or oxypropylene (-CH( _CH3 ) _CH2O- or _CH2CH2CH2O- ) is preferred, _and oxyethylene is further preferred. As the anion of the ammonium salt compound, halogen atoms, sulfonates, borates _, phosphates, etc. can be cited, among which halogen atoms and sulfonates are preferred. As the halogen atom, chlorides, bromides _, and iodides are particularly preferred, and as the sulfonate, organic sulfonates having 1 to 20 carbon atoms are particularly preferred. As the organic sulfonate, alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates can be cited. The alkyl group of the alkyl sulfonate may also have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy, acyl, and aryl groups. Specifically, the alkyl sulfonate includes methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate. The aryl group of the aryl sulfonate includes benzene ring, naphthyl ring, and anthracene ring. The benzene ring, naphthyl ring, and anthracene ring may also have a substituent, and as the substituent, a straight or branched alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms is preferred. Specific examples of the linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl, and cyclohexyl groups. Examples of other substituents include alkoxy groups having 1 to 6 carbon atoms, halogen atoms, cyano groups, nitro groups, acyl groups, and acyloxy groups.

The amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group refer to the amine compound or the ammonium salt compound having a phenoxy group at the end of the alkyl group on the opposite side to the nitrogen atom. The phenoxy group may also have a substituent. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylate group, a sulfonate group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. The substitution position of the substituent may be any one of the 2nd to 6th positions. The number of the substituents may be any one in the range of 1 to 5.

It is preferred that there is at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number _of oxyalkylene groups in the molecule is 1 or more, preferably 3 to 9, more preferably 4 to 6. Among the oxyalkylene groups, oxyethylene ( _-CH2CH2O- ) or oxypropylene (-CH( _CH3 ) _{CH2O- or -CH2CH2CH2O-} ) is preferred, and _oxyethylene is more preferred.

The amine compound having a phenoxy group can be obtained by heating a primary or secondary amine having a phenoxy group and a halogen alkyl ether to react them, adding an aqueous solution of a strong salt such as sodium hydroxide, potassium hydroxide, or tetraalkylammonium, and extracting with an organic solvent such as ethyl acetate or chloroform. Alternatively, the amine compound can be obtained by heating a primary or secondary ammonium and a halogen alkyl ether having a phenoxy group at the end to react them, adding an aqueous solution of a strong salt such as sodium hydroxide, potassium hydroxide, or tetraalkylammonium, and extracting with an organic solvent such as ethyl acetate or chloroform.

(Compound (PA) that generates a compound having a proton acceptor functional group and decomposes by irradiation with actinic rays or radiation, and the proton acceptor property decreases, disappears, or changes from proton acceptor property to acidic property) The composition of the present invention may further include a compound having a proton acceptor functional group and decomposes by irradiation with actinic rays or radiation, and the proton acceptor property decreases, disappears, or changes from proton acceptor property to acidic property [hereinafter, also referred to as compound (PA)].

The proton acceptor functional group is a functional group having a group or electron that can electrostatically interact with a proton, and for example, it refers to a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group having a nitrogen atom having an unshared electron pair that does not contribute to π-conjugation. The nitrogen atom having an unshared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula.

[Chemical formula 63]

Preferred partial structures of the proton acceptor functional group include, for example, crown ethers, nitrogen-doped crown ethers, primary to tertiary amines, pyridine, imidazole, and pyridine-like structures.

Compound (PA) produces a compound whose proton acceptor property decreases, disappears, or changes to acidic property by decomposition due to irradiation with actinic rays or radiation. Here, the decrease, disappearance, or change to acidic property of proton acceptor refers to the change of proton acceptor property caused by the addition of proton to the proton acceptor functional group. Specifically, it means that when a proton addition product is generated from a compound (PA) having a proton acceptor functional group and a proton, the equilibrium constant in the chemical equilibrium decreases.

As specific examples of compound (PA), for example, the following compounds can be cited. In addition, as specific examples of compound (PA), for example, those described in paragraphs 0421 to 0428 of Japanese Patent Application Publication No. 2014-041328 and paragraphs 0108 to 0116 of Japanese Patent Application Publication No. 2014-134686 can be cited, and these contents are incorporated into this specification.

[Chemical formula 64]

[Chemical formula 65]

[Chemical formula 66]

These alkaline compounds may be used alone or in combination of two or more.

The amount of the alkaline compound used is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the inhibitor composition.

The ratio of the photoacid generator to the alkaline compound in the composition is preferably 2.5 to 300 (molar ratio). That is, from the perspective of sensitivity and resolution, a molar ratio of 2.5 or more is preferred, and from the perspective of suppressing the decrease in resolution caused by the coarsening of the resist pattern over time until the post-exposure heat treatment, a molar ratio of 300 or less is preferred. The photoacid generator/alkaline compound (molar ratio) is more preferably 5.0 to 200, and further preferably 7.0 to 150.

As the alkaline compound, for example, compounds described in paragraphs 0140 to 0144 of JP-A-2013-011833 (amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc.) can be used.

<Hydrophobic resin> In addition to the above-mentioned resin (A), the resist composition may also have a hydrophobic resin (A'). The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film, but unlike the surfactant, it is not necessary to have a hydrophilic group in the molecule and may not work for the uniform mixing of polar/non-polar substances. As the effect of adding a hydrophobic resin, it is possible to cite the control of the static/dynamic contact angle of the resist film surface with respect to water, the suppression of degassing, etc.

From the perspective of uneven distribution on the membrane surface, the hydrophobic resin preferably has any one or more of "fluorine atoms", "silicon atoms" and "CH ₃ partial structures contained in the side chain of the resin", and more preferably has two or more of them. In addition, the hydrophobic resin preferably contains a carbon group with a carbon number of 5 or more. These groups may exist in the main chain of the resin or may be substituted in the side chain.

When the hydrophobic resin contains fluorine atoms and/or silicon atoms, the fluorine atoms and/or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin or in the side chain.

When the hydrophobic resin contains fluorine atoms, a resin having an alkyl group having fluorine atoms, a cycloalkyl group having fluorine atoms, or an aryl group having fluorine atoms as a partial structure having fluorine atoms is preferred. The alkyl group having fluorine atoms (preferably having 1 to 10 carbon atoms, more preferably having 1 to 4 carbon atoms) is a straight or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and may further have a substituent other than a fluorine atom. The cycloalkyl group having fluorine atoms is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and may also have a substituent other than a fluorine atom. As the aryl group having fluorine atoms, there can be exemplified those in which at least one hydrogen atom of an aryl group such as a phenyl group and a naphthyl group is substituted by a fluorine atom, and may also have a substituent other than a fluorine atom. As examples of repeating units having fluorine atoms or silicon atoms, those exemplified in paragraph 0519 of US2012/0251948A1 can be cited.

As mentioned above, it is preferred that the hydrophobic resin contains a _CH3 partial structure in the side chain portion. Here, the _CH3 partial structure of the side chain portion in the hydrophobic resin includes a _CH3 partial structure of an ethyl group, a propyl group, etc. On the other hand, a methyl group directly bonded to the main chain of the hydrophobic resin (e.g., an α-methyl group having a repeating unit of a methacrylic acid structure) is affected by the main chain and has a small effect on the surface non-uniformity of the hydrophobic resin, and is therefore considered to be included in the _CH3 partial structure in the present invention.

Regarding the hydrophobic resin, reference can be made to the description in <0348> to <0415> of Japanese Patent Application Laid-Open No. 2014-010245, and the contents are incorporated into this specification.

In addition, as the hydrophobic resin, those described in Japanese Patent Application Laid-Open No. 2011-248019, Japanese Patent Application Laid-Open No. 2010-175859, and Japanese Patent Application Laid-Open No. 2012-032544 can also be preferably used.

<Surfactant> The resist composition may further contain a surfactant. By containing a surfactant, when using an exposure light source with a wavelength of 250nm or less, especially 220nm or less, it is possible to form a pattern with good sensitivity and resolution and fewer development defects. As the surfactant, it is particularly preferred to use a fluorine-based and/or silicon-based surfactant. As the fluorine-based and/or silicon-based surfactant, for example, the surfactant described in >0276> of the specification of U.S. Patent Application Publication No. 2008/0248425 can be cited. In addition, EFTOP EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Fluorad FC430, 431 or 4430 (manufactured by Sumitomo 3M Limited); MEGAFAC F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by ASAHI GLASS CO., LTD.); TroySol S-366 (manufactured by Troy Chemical Industriesm, Inc.); GF-300 or GF-150 (manufactured by TOAGOSEI CO., LTD.), Surflon S-393 (manufactured by SEIMI CHEMICAL CO., LTD.); EFTOP EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (manufactured by Gemco Co., Ltd.); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA Solutions Inc.); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos Corporation). In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition to the known surfactants shown above, the surfactant can also be synthesized using a fluoroaliphatic compound produced by a short-chain polymerization (telomerization) method (also called a short-chain polymer (telomer) method) or an oligomerization (oligomerization) method (also called an oligomer method). Specifically, a polymer having a fluoroaliphatic group derived from the fluoroaliphatic compound can also be used as a surfactant. The fluoroaliphatic compound can be synthesized by the method described in Japanese Patent Publication No. 2002-090991, for example. In addition, surfactants other than fluorine-based and/or silicon-based surfactants described in >0280> of the specification of U.S. Patent Application Publication No. 2008/0248425 can also be used.

These surfactants may be used alone or in combination of two or more.

When the resistor composition contains a surfactant, its content is preferably 0 to 2 mass %, more preferably 0.0001 to 2 mass %, and further preferably 0.0005 to 1 mass %, based on the total solid content of the composition.

<Other additives> The resist composition may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber and/or a compound that promotes solubility in a developer (e.g., a phenolic compound having a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

The inhibitor composition may further contain a dissolution inhibiting compound. Here, the "dissolution inhibiting compound" is a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid and whose solubility in an organic developer solution is reduced.

[Upper layer film] In the pattern forming method of the present invention, an upper layer film (top coating film) can be formed on the upper layer of the resist film. It is preferable that the upper layer film is not mixed with the resist film and can be evenly coated on the upper layer of the resist film. There is no particular limitation on the upper layer film, and a previously known upper layer film can be formed by a previously known method, for example, the upper layer film can be formed according to the description in paragraphs 0072 to 0082 of Japanese Patent Publication No. 2014-059543.

[Content of organic impurities] When a treatment liquid containing an organic solvent containing organic impurities is used in a semiconductor device manufacturing process, organic impurities with a high boiling point of 300°C or more do not volatilize but remain therein, and are likely to become a significant cause of substrate defects. In particular, the organic impurities with a boiling point of 300°C or more are specifically considered to be resin components or plasticizers contained in plastic materials (e.g., O-rings, etc.) used to manufacture components of the device, and are presumed to be dissolved into the liquid at some point in the manufacturing process. It was confirmed that the content of the organic impurities having a boiling point of 300°C or higher relative to the total mass of the processing liquid is within a range of 0.001 to 50 ppm by mass, which is within the range of defects that can be reduced by improving the processing conditions of the developing process or the rinsing process when used in the semiconductor device manufacturing process. In the processing liquid, the content of the organic impurities having a boiling point of 300°C or higher relative to the total mass of the processing liquid is more preferably 0.001 to 30 ppm by mass, and from the viewpoint of suppressing defects of the substrate when used in the semiconductor device manufacturing process, 0.001 to 15 ppm by mass is further preferred, 0.001 to 10 ppm by mass is further preferred, and 0.001 to 1 ppm by mass is the most preferred.

From the perspective of preventing the organic impurities from not volatile and remaining on the substrate surface to cause defects when the treatment liquid is used as a developer and contacts the substrate, the content of the organic impurities with a boiling point of 300°C or more is preferably 30 ppm or less relative to the total mass of the treatment liquid. From the perspective of preventing the organic impurities with a boiling point of 300°C or more from remaining on the substrate after the baking step and suppressing the cause of defects (poor development) when the treatment liquid is used as a developer and contacts the substrate, the content of the organic impurities with a boiling point of 300°C or more is preferably 5 ppm or less relative to the total mass of the treatment liquid. In the treatment liquid, as organic impurities above 300°C, components such as dioctyl phthalate (DOP, boiling point 385°C) eluted from the O-ring, diisononyl phthalate (DINP, boiling point 403°C), dioctyl adipate (DOA, boiling point 335°C), dibutyl phthalate (DBP, boiling point 340°C), and ethylene propylene diene rubber (EPDM, boiling point 300-450°C) were confirmed.

The content of organic impurities having a boiling point of 300°C or more in the treatment liquid is measured by DI-MS (Direct Injection Mass Chromatography). As a method for setting the content of organic impurities having a boiling point of 300°C or more in the treatment liquid within the above range, the method listed in the purification step described later can be listed.

<Metallic components containing elements selected from Fe, Cr, Ni and Pb (metallic impurities)> The content of metallic impurities in the treatment solution of the present invention is preferably as small as possible. In particular, the content of each metallic component containing elements selected from Fe, Cr, Ni and Pb in the treatment solution is preferably 0.001 to 100 mass ppt relative to the total mass of the treatment solution. Metallic components exist to a certain extent in organic solvents, and are sometimes mixed into the treatment solution through them. This time, it was found that the metallic components containing elements selected from Fe, Cr, Ni and Pb contained in the treatment solution have a particularly large impact on defect performance. As long as the content of the metal component containing an element selected from Fe, Cr, Ni and Pb is less than 100 mass ppt relative to the total mass of the treatment liquid, the defect suppression ability is excellent, and when it is less than 1 mass ppt, a more significant defect suppression effect can be obtained. In addition, when the content of the metal component containing an element selected from Fe, Cr, Ni and Pb exceeds 100 mass ppt relative to the total mass of the treatment liquid, metal particles (deterioration of defects) will occur. If it exceeds 0.001 mass ppt, stable manufacturing management can be performed, so the quality of each manufacturing batch is stable. When multiple metal components containing elements selected from Fe, Cr, Ni and Pb are contained, it is better that the total amount is less than the above range. The content of metal impurities in the treatment solution is measured using ICP-MS (Inductively Coupled Plasma Mass Spectrometer). In addition, when the content is less than 1 ppt, it is difficult to measure with the original solution, so the treatment solution can be concentrated as needed for measurement. As a method for setting the content of metal impurities in the treatment solution within the above range, the methods listed in the purification step described later can be listed (for example, filtration treatment using ion exchange resin or metal adsorption component, etc.).

(Substrate) The "substrate" mentioned in the present invention includes, for example, a semiconductor substrate composed of a single layer and a semiconductor substrate composed of multiple layers. The material constituting the semiconductor substrate composed of a single layer is not particularly limited, and is generally preferably composed of III-V compounds such as silicon, silicon germanium, GaAs, or any combination thereof. When it is a semiconductor substrate composed of multiple layers, its structure is not particularly limited, for example, an integrated circuit structure such as an interconnect feature such as a metal wire and a dielectric material can be exposed on the semiconductor substrate of the above silicon. Examples of metals and alloys used in the interconnect structure include aluminum and copper, alloy aluminum, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten, but are not limited thereto. In addition, the semiconductor substrate may also have an interlayer dielectric layer, silicon oxide, silicon nitride, silicon carbide, and carbon-doped silicon oxide.

<Processing liquid manufacturing method> In order to set the content of metal components, organic impurities with a boiling point of 300°C or above, and water within the desired range, it is preferred that the processing liquid of the present invention be subjected to the following purification steps.

(Purification step) The purification step can be performed at any time. As the purification step, for example, the following purification treatments I to IV can be listed. That is, purification treatment I is a treatment for purifying the raw materials used in the manufacture of the organic solvent before manufacturing the organic solvent constituting the treatment solution. In addition, purification treatment II is a treatment for purifying the organic solvent when and/or after manufacturing the organic solvent constituting the treatment solution. In addition, purification treatment III is a treatment for purifying each component before mixing two or more organic solvents when manufacturing the treatment solution. In addition, purification treatment IV is a treatment for purifying the mixture after mixing two or more organic solvents when manufacturing the treatment solution. As described above, it is preferable to purify the target treatment liquid. Regarding purification, each organic solvent can be mixed after purification, or it can be purified after mixing each organic solvent. In particular, from the perspective of being able to make the blending ratio of the organic solvent constant, the method of blending the purified organic solvent is better. Purification treatments I to IV can be performed only once, or twice or more. In addition, as the organic solvent used, a high-purity grade product (especially one with a low content of the above-mentioned organic impurities, metal impurities, water, etc.) can be purchased and used after further subjecting it to the purification treatment described below.

An example of a purification step is shown below. In the following description, the object of purification in the purification step is referred to as "purified liquid". As an example of a purification step, the following treatments can be listed in sequence: a first ion exchange treatment, in which an ion exchange treatment is performed on the purified liquid; a dehydration treatment, in which the purified liquid after the first ion exchange treatment is dehydrated; a distillation treatment, in which the purified liquid after the dehydration treatment is distilled; a second ion exchange treatment, in which an ion exchange treatment is performed on the purified liquid after the distillation treatment; and an organic impurity removal treatment, in which organic impurities are removed from the purified liquid after the second ion exchange treatment. In addition, the above purification step is described as an example below, but the purification method for preparing the treatment solution of the present invention is not limited thereto. For example, the following treatments may be performed in sequence: first, a dehydration treatment is performed to dehydrate the purified solution; a distillation treatment is performed to distill the purified solution after the dehydration treatment; a first ion exchange treatment is performed to perform an ion exchange treatment on the purified solution; and an organic impurity removal treatment is performed to remove organic impurities from the purified solution after the second ion exchange treatment.

According to the first ion exchange treatment, ion components (such as metal components, etc.) in the purified liquid can be removed. In the first ion exchange treatment, a first ion exchange mechanism such as an ion exchange resin is used. As the ion exchange resin, any one of a cation exchange resin or anion exchange resin is set in a single bed, a cation exchange resin and anion exchange resin are set in multiple beds, and a cation exchange resin and anion exchange resin are set in a mixed bed. In addition, as the ion exchange resin, in order to reduce the water elution from the ion exchange resin, it is better to use a dry resin that contains as much water as possible. As such a dry resin, commercially available products can be used, and examples thereof include 15JS-HG•DRY (trade name, dry cation exchange resin, moisture content 2% or less) and MSPS2-1•DRY (trade name, mixed bed resin, moisture content 10% or less) manufactured by Organo Corporation.

By dehydration treatment, water in the purified liquid can be removed. In addition, when the zeolite described later (especially, molecular sieve (trade name) manufactured by UNION SHOWA K.K., etc.) is used in the dehydration treatment, olefins can also be removed. As dehydration mechanisms used in the dehydration treatment, there can be listed dehydration membranes, water adsorbents insoluble in the purified liquid, aeration replacement devices and heating using dry inert gas, or vacuum heating devices, etc. When using a dehydration membrane, membrane dehydration based on osmotic evaporation (PV) or vapor permeation (VP) is performed. The dehydration membrane is, for example, constituted as a water-permeable membrane module. As dehydration membranes, membranes made of polymer materials such as polyimide, cellulose, and polyvinyl alcohol, or inorganic materials such as zeolite can be used. Water adsorbents are used by adding them to the extracted liquid. Examples of water adsorbents include zeolite, phosphorus pentoxide, silica gel, calcium chloride, sodium sulfate, magnesium sulfate, zinc chloride anhydride, fuming sulfuric acid, and alkaline lime.

According to the distillation treatment, impurities eluted from the dehydration membrane, metal components in the purified liquid that are difficult to remove in the first ion exchange treatment, fine particles (including when the metal components are fine particles), and water in the purified liquid can be removed. The distillation mechanism is composed of, for example, a single-stage distillation device. By the distillation treatment, impurities are concentrated in the distillation device, etc., but in order to prevent part of the concentrated impurities from flowing out, it is better to set a mechanism on the distillation mechanism to discharge part of the concentrated impurity liquid to the outside regularly or stably.

According to the second ion exchange treatment, when the impurities accumulated in the distillation device flow out, they can be removed or the elution from the stainless steel (SUS) pipe used as the liquid transport pipe can be removed. As the second ion exchange mechanism, a tower-shaped container filled with an ion exchange resin and an ion adsorption membrane can be listed. From the perspective of being able to treat at a high flow rate, the ion adsorption membrane is preferred. As an ion adsorption membrane, NEOSEPTA (trade name, manufactured by ASTOM Corporation) can be listed.

The above treatments are preferably carried out in a closed state and in an inert gas atmosphere where the possibility of water mixing into the purified liquid is low. In order to suppress the mixing of water as much as possible, it is better to carry out each treatment in an inert gas atmosphere with a dew point temperature of -70°C or less. The reason is that in an inert gas atmosphere below -70°C, the water concentration in the gas phase is less than 2 mass ppm, so the possibility of water mixing into (the purified liquid) becomes low.

As a purification step, in addition to the above-mentioned treatment, there can be cited the adsorption purification treatment of metal components using silicon carbide described in International Publication No. WO2012/043496.

According to the organic impurity removal treatment, high-boiling point organic impurities (including organic impurities with a boiling point of 300°C or more) contained in the purified liquid after the distillation treatment and which are difficult to remove in the distillation treatment can be removed. As an organic impurity removal mechanism, for example, it can be implemented by an organic impurity adsorption component having an organic impurity adsorption filter capable of adsorbing organic impurities. In addition, the organic impurity adsorption component is usually composed of the above-mentioned organic impurity adsorption filter and a substrate for fixing the above-mentioned impurity adsorption filter. From the perspective of improving the adsorption performance of organic impurities, it is preferable that the organic impurity adsorption filter has an organic skeleton on the surface that can interact with organic impurities (in other words, the surface is modified by the organic skeleton that can interact with organic impurities). In addition, as an example of the organic skeleton on the surface that can interact with organic impurities, the surface of the substrate constituting the organic impurity adsorption filter described later is given the morphology of the organic skeleton that can interact with the above-mentioned organic impurities. As an organic skeleton that can interact with organic impurities, for example, a chemical structure that reacts with organic impurities and can capture organic impurities in the organic impurity adsorption filter can be listed. More specifically, when the organic impurities include dioctyl phthalate, diisononyl phthalate, dioctyl adipate or dibutyl phthalate, the organic skeleton can be a benzene ring skeleton. Also, when the organic impurities include EPDM rubber, the organic skeleton can be an extended alkyl skeleton. Also, when the organic impurities include n-long-chain alkyl alcohol (structural isomer when 1-long-chain alkyl alcohol is used as a solvent), the organic skeleton can be an alkyl group. As the substrate (material) constituting the organic impurity adsorption filter, cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene and fluororesin carrying activated carbon can be listed. Furthermore, as an organic impurity removal filter, a filter in which activated carbon is adhered to a non-woven fabric as described in Japanese Patent Application Publication No. 2002-273123 and Japanese Patent Application Publication No. 2013-150979 can also be used.

Furthermore, the above-mentioned organic impurity removal treatment is not limited to the use of an organic impurity adsorption filter capable of adsorbing organic impurities as described above, and may also be a form of physically capturing organic impurities. Most organic impurities with a high boiling point of more than 250°C are relatively large (for example, compounds with a carbon number of more than 8), and therefore can also be physically captured by using a filter with a pore size of about 1nm. For example, when dioctyl phthalate is contained as an organic impurity, the structure of dioctyl phthalate is larger than 10Å (=1nm). Therefore, by using an organic impurity removal filter with a pore size of 1nm, dioctyl phthalate cannot pass through the pores of the filter. That is, dioctyl phthalate is physically captured by the filter and thus removed from the purified material. In this way, organic impurities can be removed not only by chemical interaction but also by physical removal methods. However, in this case, filters with pore sizes of 3 nm or more are used as "filter members" described later, and filters with pore sizes of less than 3 nm are used as "organic impurity removal filters." In this manual, 1Å (angstrom) is equivalent to 0.1nm.

Furthermore, the purification step of the present invention may further include, for example, purification treatment V and purification treatment VI described below. Purification treatment V and purification treatment VI may be performed at any time, for example, after purification step IV is performed. Purification treatment V is a filtration treatment using a metal ion adsorption component for the purpose of removing metal ions. Furthermore, purification treatment VI is a filtration treatment for removing coarse particles. Purification treatment V and purification treatment VI are described below.

In purification treatment VI, as an example of a metal ion removal mechanism, filtration using a metal ion adsorption component having a metal ion adsorption filter can be cited. The metal ion adsorption component is a structure having at least one metal ion adsorption filter, and may also be a structure in which a plurality of metal ion adsorption filters are stacked according to the desired purification level. The metal ion adsorption component is usually composed of the above-mentioned metal ion adsorption filter and a substrate for fixing the above-mentioned metal ion adsorption filter. The metal ion adsorption filter has the function of adsorbing metal ions in the purified liquid. In addition, the metal ion adsorption filter is preferably a filter capable of ion exchange. Here, there is no particular limitation on the metal ions to be adsorbed, but Fe, Cr, Ni and Pb are preferred from the viewpoint of being the cause of defects in semiconductor devices. From the viewpoint of improving the adsorption performance of metal ions, the metal ion adsorption filter preferably has an acid group on the surface. Examples of the acid group include sulfonic group and carboxyl group. As the substrate (material) constituting the metal ion adsorption filter, examples include cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene and fluororesin.

In purification treatment VI, as an example of a filtering mechanism, a filtering member having a filter with a particle size of 20 nm or less can be cited. By adding the above-mentioned filter, particulate impurities can be removed from the purified liquid. Here, as "particulate impurities", particles of dust, ash, organic solids, and inorganic solids contained as impurities in the raw materials used in the production of the purified liquid, and particles of dust, ash, organic solids, and inorganic solids that are included as contaminants when purifying the purified liquid can be cited, but those that are not dissolved in the purified liquid and exist as particles also belong to this. In addition, "particulate impurities" also include colloidal impurities containing metal atoms. There is no particular limitation on the metal atoms. When the content of at least one metal atom selected from Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn and Pb (preferably Fe, Cr, Ni and Pb) is particularly low (for example, when the content of the above metal atoms in the purified liquid is less than 1000 mass ppt), impurities containing these metal atoms are easy to colloidal. It is difficult to remove the colloidal impurities by the above metal ion adsorption component. Therefore, by using a filter with a particle size of less than 20nm (for example, a precision filter membrane with a pore size of less than 20nm), the colloidal impurities can be effectively removed. Particulate impurities have a size that can be removed by a filter with a particle size of 20 nm or less, specifically, particles with a diameter of 20 nm or more. In addition, in this specification, particulate impurities are sometimes referred to as "coarse particles". Among them, the particle size of the above-mentioned filter is preferably 1 to 15 nm, and 1 to 12 nm is more preferably. If the particle size is 15 nm or less, it can remove finer particulate impurities, and if the particle size is 1 nm or more, the filtration efficiency of the purified liquid is improved. Here, the particle size refers to the minimum size of particles that the filter can remove. For example, when the particle size of the filter is 20 nm, it can remove particles with a diameter of 20 nm or more. Examples of the material of the filter include 6-nylon, 6,6-nylon, polyethylene, polypropylene, polystyrene, and fluororesin.

The filter component may further include a filter for removing particles with a pore size of 50 nm or more (eg, a precision filter membrane for removing particles with a pore size of 50 nm or more). When the liquid to be purified contains microparticles in addition to colloidal impurities, especially colloidal impurities containing metal atoms such as iron or aluminum, the liquid to be purified is filtered using a filter with a particle size of 50 nm or more (e.g., a precision filter membrane with a pore size of 50 nm or more) before filtering using a filter with a particle size of 20 nm or less (e.g., a precision filter membrane with a pore size of 20 nm or less), thereby improving the filtering efficiency of the filter with a particle size of 20 nm or less (e.g., a precision filter membrane with a pore size of 20 nm or less) and further improving the removal performance of coarse particles.

The purified liquid obtained through each of these treatments can be used in the composition of the treatment liquid of the present invention or directly used as the treatment liquid of the present invention. In addition, as an example of the above purification step, the case where all the treatments are performed is shown, but it is not limited to this. Each of the above treatments can be performed individually or in combination. In addition, each of the above treatments can be performed once or multiple times.

In addition to the above purification step, as a method for setting the content of organic impurities with a boiling point of 300°C or more, metal components and water contained in the treatment liquid within a desired range, there is a method of placing the raw materials of the organic solvent constituting the treatment liquid or the treatment liquid itself in a container from which impurities are less eluted. In addition, there is a method of lining the inner wall of the "pipes" etc. in order to prevent the metal components from eluting from the "pipes" when the treatment liquid is produced.

[Container (storage container)] The treatment liquid of the present invention can be stored, transported and used by filling in any container as long as the corrosiveness etc. is not a problem. As a container, a semiconductor container is preferably one with high cleanliness inside the container and less elution of impurities. As a container that can be used, specifically, the "clean bottle" series manufactured by AICELLO CORPORATION and the "pure bottle" manufactured by KODAMA PLASTICS Co., Ltd. can be listed, but it is not limited to these. The inner wall of the container (the liquid contact part that contacts the solution in the container) is preferably formed of a non-metallic material. As the non-metal material, at least one selected from polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, tetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinylidene fluoride resin (PVDF), chlorotrifluoroethylene copolymer (PCTFE) and polyvinyl fluoride resin (PVF) is more preferred. In particular, when a container with an inner wall of a fluorine-based resin is used in the above, compared with a container with an inner wall of polyethylene resin, polypropylene resin or polyethylene-polypropylene resin, the occurrence of adverse conditions such as the dissolution of ethylene or propylene oligomers can be suppressed. As a specific example of such a container with an inner wall made of fluorine-based resin, for example, the FluoroPure PFA composite cylinder manufactured by Entegris Inc. can be cited. In addition, the containers described in the Japanese Patent Publication No. 3-502677, page 4, etc., the International Publication No. 2004/016526, page 3, etc., and the International Publication No. 99/046309, pages 9 and 16, etc. can also be used. In addition, when the inner wall is designed as a non-metal material, it is better to suppress the dissolution of organic components in the non-metal material into the treatment liquid.

Furthermore, as the inner wall of the container, in addition to the above-mentioned non-metallic materials, quartz or metal materials (preferably metal materials that have been electrolytically polished. Metal materials that have been electrolytically polished as much as possible) can also be preferably used. The above-mentioned metal materials (especially metal materials used in the manufacture of electrolytically polished metal materials) preferably contain more than 25% by mass of chromium relative to the total mass of the metal material, for example, stainless steel. The chromium content in the metal material is preferably 30% by mass or more relative to the total mass of the metal material. In addition, there is no particular restriction as the upper limit value, and it is usually better to be 90% by mass or less.

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 (Stainless Steel, Steel Use Stainless) 304 (Ni content 8% by mass, Cr content 18% by mass), SUS304L (Ni content 9% by mass, Cr content 18% by mass), SUS316 (Ni content 10% by mass, Cr content 16% by mass), and SUS316L (Ni content 12% by mass, Cr content 16% by mass).

The method of electrolytically polishing the metal material is not particularly limited, and a known method can be adopted. 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 adopted.

It is speculated that the chromium content in the passivation layer on the surface of the metal material becomes higher than the chromium content of the parent phase by electrolytic polishing. Therefore, it is speculated that the metal component is not easy to flow into the solution from the inner wall coated with the electrolytically polished metal material, so a solution with reduced metal components (metal impurities) can be obtained. In addition, it is preferred that the metal material is polished. There is no particular restriction on the polishing method, and a known method can be adopted. There is no particular restriction on the size of the abrasive grains used in the fine polishing. From the perspective of making the surface unevenness of the metal material easier to become smaller, #400 or less is preferred. In addition, it is preferred that polishing be performed before electrolytic polishing. Furthermore, the metal material may be processed by combining one or more of the polishing, pickling and magnetic fluid polishing steps performed by changing the size and number of abrasive grains.

In the present invention, the container and the processing solution contained in the container may be referred to as a solution container.

It is preferred that the interior of such containers be cleaned before filling with the treatment liquid. When the liquid used for cleaning is the treatment liquid of the present invention itself or the organic solvent contained in the treatment liquid of the present invention, the effect of the present invention can be significantly obtained. The treatment liquid of the present invention can also be transported and stored in containers such as a gallon bottle or a QT bottle after manufacture. The gallon bottle can be made of glass or other materials.

In order to prevent the composition of the treatment liquid in storage from changing, the inside of the container can be replaced with an inert gas (nitrogen or argon, etc.) with a purity of 99.99995% by volume or more. In particular, a gas with a low water content is preferred. In addition, the temperature can be controlled within the range of -20°C to 20°C during transportation and storage to prevent deterioration.

(Clean room) It is preferred that all operations including the manufacture of the treatment liquid of the present invention, the opening and/or cleaning of the storage container, the filling of the treatment liquid, the processing analysis and the measurement are all performed in a clean room. It is preferred that the clean room meets the 14644-1 clean room standard. It is preferred that it meets any of ISO (International Organization for Standardization) Grade 1, ISO Grade 2, ISO Grade 3 and ISO Grade 4, and it is more preferred that it meets ISO Grade 1 or ISO Grade 2, and it is further preferred that it meets ISO Grade 1. The manufacture of the treatment liquid, the opening and/or cleaning of the storage container, the filling of the treatment liquid, the processing analysis and the measurement in the embodiments described below are performed in a clean room of Grade 2.

(Filtration) In order to set the content of organic impurities with a boiling point of 300°C or more, metal components and water within the desired range, or to remove foreign matter and coarse particles, the treatment liquid of the present invention or the organic solvent contained in the treatment liquid is preferably filtered. The filter used in the filtration is not particularly limited in use as long as it has been used for filtering purposes. Examples of materials constituting the filter include fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (including high-density, ultra-high molecular weight) and the like. Among them, polyamide resins, PTFE and polypropylene (including high-density polypropylene) are preferred. By using a filter formed of these materials, highly polar foreign matter that is likely to cause particle defects can be removed more effectively, and the amount of metal components (metal impurities) can also be reduced more effectively.

As for the critical surface tension of the filter, the lower limit is preferably 70mN/m or more. As the upper limit, 95mN/m or less is preferred. Among them, the critical surface tension of the filter is more than 75mN/m and less than 85mN/m, which is more preferred. In addition, the value of the critical surface tension is the nominal value of the manufacturer. By using a filter with a critical surface tension in the above range, highly polar foreign matter that is likely to cause particle defects can be more effectively removed, and the amount of metal components (metal impurities) can also be more effectively reduced.

There are no special restrictions on the filter used in the filtration as long as it has been used for filtering purposes. As materials constituting the filter, for example, fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, polyolefin resins such as polyethylene and polypropylene (PP) (including high-density, ultra-high molecular weight), etc. can be listed. Among them, polypropylene (including high-density polypropylene) and nylon are preferred. The pore size of the filter is preferably about 0.001 to 1.0 μm, more preferably about 0.01 to 0.5 μm, and even more preferably about 0.01 to 0.1 μm. By setting the pore size of the filter within the above range, clogging of the filter can be suppressed, and fine foreign matter contained in the processing liquid or the organic solvent contained in the processing liquid can be reliably removed.

When using filters, different filters can also be combined. In this case, filtering using the first filter can be performed only once or twice or more. When filtering is performed twice or more using different filters, the filters can be of the same type or different types, and different types are preferred. Typically, the first filter and the second filter are preferably different in at least one of the pore size and the constituent material. Compared to the pore size of the first filtration, the pore size after the second filtration is preferably the same as or smaller than the pore size. Furthermore, first filters with different pore sizes within the above range can also be combined. The pore size here can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, it is possible to select from various filters provided by NIHON PALL LTD., Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (formerly Nippon micro squirrel Co., Ltd.), or KITZMICROFILTER CORPORATION. In addition, it is also possible to use "P-nylon filter (pore diameter 0.02 μm, critical surface tension 77 mN/m)" made of polyamide; (manufactured by NIHON PALL LTD.), "PE-clean filter (pore diameter 0.02 μm)" made of high-density polyethylene; (manufactured by NIHON PALL LTD.), and "PE-clean filter (pore diameter 0.01 μm)" made of high-density polyethylene; (manufactured by NIHON PALL LTD.).

Although there are no particular limitations, for example, in addition to the viewpoint that the effect of the treatment liquid of the present invention is more excellent, from the viewpoint of suppressing the increase of particulate metals during the storage of the purified treatment liquid, the relationship between the purified liquid and the material of the filter used in the filtration is a combination of satisfying the relationship (Ra/R0) ≤ 1 between Ra and R0 when the interaction radius in the Hansen solubility parameter (HSP) space derived from the material of the filter used in the filtration is set to (R0) and the radius of the sphere in the Hansen space derived from the treatment liquid or the liquid contained in the organic solvent contained in the treatment liquid is set to (Ra), and the treatment liquid or the organic solvent contained in the treatment liquid is preferably filtered by a filter material satisfying these relationships. (Ra/R0) ≤ 0.98 is preferred, and (Ra/R0) ≤ 0.95 is more preferred. As a lower limit, 0.5 or more is preferred, 0.6 or more is more preferred, and 0.7 is further preferred. Although the mechanism is not clear, if it is within this range, the formation of particulate metal or the growth of particulate metal during long-term storage will be suppressed. There is no particular limitation on the combination of such filters and the treatment liquid or the organic solvent contained in the treatment liquid, and those in U.S. Patent Gazette No. 2016/0089622 can be cited.

The second filter can be made of the same material as the first filter. It can have the same pore size as the first filter. When the pore size of the second filter is smaller than that of the first filter, the ratio of the pore size of the second filter to the pore size of the first filter (pore size of the second filter/pore size of the first filter) is preferably 0.01 to 0.99, more preferably 0.1 to 0.9, and even more preferably 0.2 to 0.9. By setting the pore size of the second filter to the above range, fine foreign matter mixed in the solution is more reliably removed.

In the present invention, when the content of one or more metal elements selected from Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Pd and Zn is particularly low relative to the treatment solution or the organic solvent contained in the treatment solution (for example, when the content of the above metal elements relative to the treatment solution or the organic solvent contained in the treatment solution is 1000 mass ppt or less), impurities containing these metal elements tend to be easily colloidal. Therefore, it is easy to make it difficult to remove the colloidal impurities in the ion adsorption film. Therefore, the inventors of the present invention have found that the colloidal impurity components can be removed by using a precision filter membrane with a pore size of 20nm or less for purification.

Furthermore, when the treatment liquid or the organic solvent contained in the treatment liquid contains microparticles in addition to colloidal impurities (especially colloidal impurities containing metal elements such as iron or aluminum), it is better to purify it by filtering it with a precision filter membrane for removing microparticles with a pore size of 50 nm or more before filtering it with a precision filter membrane with a pore size of 20 nm or less.

The treatment liquid of the present invention or the organic solvent contained in the treatment liquid is preferably purified by an ion adsorption mechanism in addition to the filter as described above. The ion adsorption mechanism is preferably an ion adsorption mechanism modified with anionic groups such as sulfonic groups or carboxyl groups, cationic groups, or both on the surface of cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, or fluororesin. The ion adsorption mechanism modified with anionic groups can remove cationic ions such as Na ions and Ca ions, and the ion adsorption mechanism modified with cationic groups can remove anionic ions such as Cl ions and acid components. The ion adsorption mechanism may use anionic groups, cationic groups, or a combination of both, depending on the purpose. The ion adsorption mechanism may also be a filter.

The above filtering steps can also be repeated several times according to the purpose.

Furthermore, it is preferred that the filter used is treated before filtering the treatment liquid or the organic solvent contained in the treatment liquid. The liquid used in the treatment is not particularly limited, but if it is an organic solvent contained in the treatment liquid of the present invention, the desired effect of the present invention can be significantly obtained.

When filtering, the upper limit of the temperature during filtering is preferably below room temperature (25°C), more preferably below 23°C, and further preferably below 20°C. In addition, the lower limit of the temperature during filtering is preferably above 0°C, more preferably above 5°C, and further preferably above 10°C. During filtering, particulate foreign matter or impurities can be removed, but if the filtering is performed at the above temperature, the amount of particulate foreign matter or impurities dissolved in the treatment liquid or the organic solvent contained in the treatment liquid is reduced, so the filtering is performed more effectively.

In particular, from the perspective of adjusting the content of metal components (metal impurities), it is better to filter at the above temperature. Although the mechanism is not clear, it is believed that metal components (metal impurities) are mostly present in a particulate colloidal state. It is believed that if filtering is performed at the above temperature, part of the metal components (metal impurities) floating in a colloidal state will aggregate, and the aggregates are effectively removed by filtering, so it is easy to adjust the content of metal components (metal impurities) to a specified amount.

Filter pressure affects filtration accuracy, so it is better to keep the pressure pulsation as small as possible during filtration.

In the preparation and purification of the treatment liquid or the organic solvent contained in the treatment liquid of the present invention, there is no special restriction on the filtration speed, but from the perspective of the better effect of the present invention, 0.6L/min/ ^m2 or more is preferred, 0.75L/min/ ^m2 or more is more preferred, and 1.0L/min/ ^m2 or more is further preferred. A pressure difference that guarantees the filter performance (the filter is not damaged) is set in the filter. When this value is larger, the filtration speed can be increased by increasing the filtration pressure. That is, the upper limit of the above-mentioned filtration speed usually depends on the pressure difference of the filter, and it is usually better to be 10.0L/min/ ^m2 or less.

In the preparation and purification of the treatment liquid of the present invention or the organic solvent contained in the treatment liquid, from the viewpoint of the better effect of the present invention, the filtration pressure is preferably 0.001MPa or more and 1.0MPa or less, 0.003MPa or more and 0.5MPa or less, and 0.005MPa or more and 0.3MPa or less. In particular, when a filter with a small pore size is used, the amount of particulate foreign matter or impurities dissolved in the solution can be effectively reduced by increasing the filtration pressure. When a filter with a pore size of less than 20nm is used, it is particularly preferable to set the filtration pressure to 0.005MPa or more and 0.3MPa or less.

Furthermore, if the pore size of the filter membrane is reduced, the filtration rate is reduced. For example, by connecting a plurality of filters equipped with the same type of filter membrane in parallel, the filtration area is enlarged and the filtration pressure is reduced, thereby compensating for the reduction in filtration rate.

[De-electrification step] The preparation and purification of the treatment liquid of the present invention or the organic solvent contained in the treatment liquid may further include a de-electrification step. The de-electrification step is a step of de-electrifying at least one selected from the raw materials, reactants and purified products (hereinafter referred to as "purified products, etc.") to reduce the electrostatic potential of the purified products, etc. There is no particular limitation on the de-electrification method, and a known de-electrification method can be adopted. As a de-electrification method, for example, a method of contacting the above-mentioned purified solution, etc. with a conductive material can be listed. The time for contacting the above-mentioned purified solution, etc. 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 the conductive material, stainless steel, gold, platinum, diamond, and glassy carbon can be cited. As a method of making the purified liquid contact the conductive material, for example, a method of placing a grounded screen made of a conductive material inside a pipeline and passing the purified liquid through the screen can be cited.

The above-mentioned charge removal step can also be implemented at any time from the raw material supply to the filling of the purified product, for example, it is preferably set before at least one step selected from the raw material supply step, reaction step, liquid adjustment step, purification step, filtration step and filling step. In particular, it is preferable to perform the charge removal step before injecting the purified product into the container used in each of the above steps. Thereby, it is possible to suppress the mixing of impurities from the container, etc. into the purified product, etc. [Example]

The present invention is further specifically described below by way of examples, but the present invention is not limited to the following examples as long as it does not deviate from the gist thereof. In addition, unless otherwise specified, "part" and "%" are based on mass. In addition, the processing liquid used in the subsequent development or rinsing is subjected to quantitative analysis of sulfur compounds (for example, measured by the method specified in JIS K2541-6: 2013 "Sulfur component test method (ultraviolet fluorescence method)") and quantitative analysis of phosphorus compounds (measured as total phosphorus by absorptiometry according to the method specified in JIS K0102: 2013), and the results can confirm that these compounds are substantially not contained. In addition, “does not substantially contain” means that when the content (concentration) of such compounds is measured by a method capable of measuring the content (concentration) of such compounds, such compounds are not detected (less than the detection limit).

[Preparation of Inhibitor Composition 1] [Various Components] <Resin (A) etc.> As resin (A), the following resin (A-1) was used. In addition, the molar ratio of each repeating unit in the following resin (A-1) was 40/30/30 from left to right. The above molar ratio was calculated by ¹ H-NMR (Nuclear Magnetic Resonance) measurement. In addition, the weight average molecular weight (Mw) of standard polystyrene converted based on gel permeation chromatography (GPC) (solvent: THF) of resin (A) was 12,000, and the molecular weight dispersion (Mw/Mn) was 1.5.

[Chemical formula 67]

<Photoacid generator> As a photoacid generator, the photoacid generator (B-1) shown below was used.

[Chemical formula 68]

<Acid diffusion control agent> As the acid diffusion control agent, the acid diffusion control agent (E-1) shown below was used.

[Chemical formula 69]

<Solvent> As solvents, the following solvents were used. C-1: Propylene glycol monomethyl ether acetate C-2: Ethyl lactate

[Preparation of Resist Composition 1] 0.77 g of the above resin (A-1), 0.2 g of the above photoacid generator (B-1) and 0.03 g of the above acid diffusion control agent (E-1) were dissolved in 675 g of the above solvent (C-1) and 7.5 g of the above solvent (C-2). This was filtered using a polyethylene filter having a pore size of 0.03 μm to obtain Resist Composition 1.

[Pattern formation (EUV exposure, negative development) and evaluation 1] [Pattern formation] <Resist film formation> The above-mentioned resist composition 1 was applied on a 12-inch silicon wafer and baked (PB) at 120°C for 60 seconds to form a resist film with a thickness of 40nm.

<Exposure> The resist film-coated wafers were subjected to EUV exposure using NA (Numerical Aperture) 0.25 and dipole illumination (Dipole 60x, outer sigma 0.81, inner sigma 0.43). Specifically, EUV exposure was performed by changing the exposure amount through a mask including a pattern formed on the wafer with dimensions of (1) a line and space pattern with a pitch of 40 nm and a width of 20 nm (equivalent to the mask for forming a "dense pattern" in Tables 2, 4, 6, 8, 10, and 12) or (2) a line and space pattern with a pitch of 108 nm and a width of 20 nm (equivalent to the mask for forming a "sparse pattern" in Tables 2, 4, 6, 8, 10, and 12). After irradiation, the wafer was taken out from the EUV exposure device and immediately baked (PEB) at 90°C for 60 seconds.

<Development> After that, the wafer was rotated at 50 rpm using a spray-type developer (ADE3000S manufactured by ACTES Co., Ltd.) while spraying a developer (23°C) at a flow rate of 200 mL/min for 30 seconds. In addition, butyl acetate was used as the developer.

<Rinsing> (Preparation of treatment liquid) As shown in Tables 1, 3, 5, 7, 9, and 11 described below, each treatment liquid was prepared by mixing the first organic solvent and the second organic solvent at a predetermined ratio. In addition, as the first organic solvent and the second organic solvent used in each treatment liquid, semiconductor grade was used. Each treatment liquid obtained was used as a rinse liquid in the rinse treatment described below.

(Rinsing treatment) After that, while rotating the wafer at 50 revolutions (rpm), each treatment liquid (23°C) listed in Table 1, Table 3, Table 5, Table 7, Table 9 and Table 11 described later was sprayed at a flow rate of 200 mL/min for 15 seconds to perform a rinsing treatment. Finally, the wafer was dried by high-speed rotation at 2000 revolutions (rpm) for _TR seconds. In addition, the above-mentioned " _TR seconds" is the drying time (seconds) listed in the "Drying time (seconds)" column in Table 1, Table 3, Table 5, Table 7, Table 9 and Table 11 + 20 seconds. That is, in the case of Example 1, " _TR seconds" is 60 seconds (that is, 40 seconds + 20 seconds).

[Evaluation Test] The wafers were exposed, developed, and rinsed, and the following items were evaluated for performance.

<Evaluation of drying time> The evaluation of the drying time of the treatment liquid was carried out in the following order. It is generally believed that the longer the drying time of the treatment liquid, the greater the influence caused by the capillary force and the faster the collapse. Therefore, the shorter the drying time of the treatment liquid, the more the pattern collapse can be suppressed, which is better. In the evaluation of the drying time, the time required for the solvent to dry was observed by naked eyes when each treatment liquid (23°C) listed in Table 1, Table 3, Table 5, Table 7, Table 9 and Table 11 was sprayed at a flow rate of 200 mL/min for 5 seconds while rotating the wafer at 50 rpm and drying was performed at 2000 rpm. The results are shown in "Drying time (seconds)" in Table 1, Table 3, Table 5, Table 7, Table 9 and Table 11.

<Resolution (pattern collapse performance: dense pattern, sparse pattern)> The resolution of line and space patterns exposed at different exposure amounts was observed using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.) at a magnification of 200k. The minimum line width that did not cause pattern collapse was found within one observed field of view and used as an indicator of pattern collapse. The smaller the value, the better the pattern collapse performance. The obtained minimum line width was evaluated using the following evaluation criteria. In addition, the pattern collapse performance was evaluated for both the pattern formed using a dense pattern forming mask and the pattern formed using a sparse pattern forming mask. In addition, in actual use, a rating of "C" or above is preferred. (Evaluation criteria) "A": Minimum line width is 16nm or less "B": Minimum line width is more than 16nm and less than 18nm "C": Minimum line width is more than 18nm and less than 20nm "D": Minimum line width is more than 20nm and less than 22nm "E": Minimum line width is more than 22nm

<Film loss in the exposed area> (Preparation of samples for evaluation) In each embodiment and comparative example, pattern formation was performed in the same manner except that the exposure conditions in the above-mentioned [Pattern formation] <Exposure> were changed to the conditions described below. In addition, a KrF excimer laser scanner was used in the following evaluation. 《Exposure conditions》 The wafer with the above-mentioned barrier film was fully exposed with an exposure amount of 40mJ (overexposure) using a KrF excimer laser scanner (manufactured by ASML, PAS5500/850C, wavelength 248nm). After exposure, the wafer was immersed in each treatment solution of the embodiment and comparative example for 10 minutes, and the dissolution amount (Å) was measured. In addition, the dissolution amount was measured by an optical film thickness meter Woollam Japan M2000. The dissolution rate (Å/min) was calculated by dividing the obtained dissolution amount (Å) by the immersion time (10 minutes), and the film loss in the exposed part was evaluated according to the following evaluation criteria. The smaller the value, the more suppressed the film loss in the exposed part. In addition, in actual use, "C" and above are preferred. (Evaluation criteria) "A": less than 3Å/min "B": 3Å/min or more and less than 10Å/min "C": 10Å/min or more and less than 20Å/min "D": 20Å/min or more and less than 40Å/min "E": 40Å/min or more

<Bridge defect suppression (dot defect defect)> A dot pattern for evaluating bridge defect suppression was prepared in the following procedure. (Resist film formation) The resist composition 1 of the embodiment and the comparative example was applied on a 12-inch silicon wafer and baked (PB) at 120°C for 60 seconds to form a resist film with a thickness of 40 nm.

(Exposure) The wafer with the resist film was exposed to EUV using NA (Numerical Aperture) 0.25 and Quasar illumination (Quasar45, outer sigma 0.81, inner sigma 0.51). Specifically, EUV exposure was performed by changing the exposure amount through a mask containing a pattern for forming a dot pattern with a pitch of 60nm and a dot size of 30nm on the wafer. After irradiation, the wafer was taken out of the EUV exposure device and immediately baked (PEB) at 90℃ for 60 seconds.

(Development) After that, a spray-type developer (ADE3000S manufactured by ACTES Co., Ltd.) was used to develop the wafer by spraying a developer (23°C) at a flow rate of 200 mL/min for 30 seconds while rotating the wafer at 50 rpm. In addition, butyl acetate was used as the developer.

(Rinsing treatment) After that, the respective treatment liquids (23°C) listed in Tables 1, 3, 5, 7, 9, and 11 described below were sprayed at a flow rate of 200 mL/min for 15 seconds while the wafer was rotated at 50 rpm, thereby performing a rinsing treatment. Finally, the wafer was dried by high-speed rotation at 2000 rpm for _TR seconds. In addition, the definition of " _TR seconds" is as described above.

(Bridge defect suppression (dot missing performance)) The resolution of the dot pattern analyzed at the optimal exposure when analyzing a dot pattern with a dot size of 30nm was observed from the top of the pattern, and the number of bridge defects (specifically, the number of dots with missing defects) generated in a 12-inch wafer was calculated and used as an indicator of bridge defect suppression. The smaller the value, the better the dot missing performance. (Evaluation criteria) “A”: The number of bridge defects is 10 or less “B”: The number of bridge defects is more than 10 and less than 20 “C”: The number of bridge defects is more than 20 and less than 50 “D”: The number of bridge defects is more than 50

＜Electro-Static Discharge (ESD)＞ The resistivity (Ω･m) of the treatment solution (temperature: 23°C) was measured using the superinsulator SM-8220 (manufactured by HIOKI E.E. CORPORATION). The obtained resistivity values were evaluated according to the following evaluation criteria. (Evaluation criteria) “A”: less than 5000Ω･m “B”: 5000Ω･m to 100,000Ω･m “C”: more than 100,000Ω･m

Furthermore, the following resolution (pattern collapse performance: DOT (dot) pattern) evaluation was performed on the treatment solutions in Tables 1, 5, 9, and 11.

<Resolution (Pattern Collapse Performance: DOT Pattern)> (Resist Film Formation) The resist composition 1 of the embodiment and the comparative example was applied on a 12-inch silicon wafer and baked (PB) at 120°C for 60 seconds to form a resist film with a thickness of 40 nm.

(Exposure) The wafer with the resist film was exposed to EUV using NA (Numerical Aperture) 0.25 and Quasar illumination (Quasar45, outer sigma 0.81, inner sigma 0.51). Specifically, EUV exposure was performed by changing the exposure amount through a mask containing a pattern for forming a dot pattern with a pitch of 60nm and a dot size of 30nm on the wafer. After irradiation, the wafer was taken out of the EUV exposure device and immediately baked (PEB) at 90℃ for 60 seconds.

(Development) After that, a spray-type developer (ADE3000S manufactured by ACTES Co., Ltd.) was used to develop the wafer by spraying a developer (23°C) at a flow rate of 200 mL/min for 30 seconds while rotating the wafer at 50 rpm. In addition, butyl acetate was used as the developer.

(Rinsing treatment) After that, the respective treatment liquids (23°C) listed in Tables 1, 5, 9, and 11 described below were sprayed at a flow rate of 200 mL/min for 15 seconds while the wafer was rotated at 50 rpm to perform rinsing treatment. Finally, the wafer was dried by high-speed rotation at 2000 rpm for _TR seconds. The definition of " _TR seconds" is as described above.

The resolution of dot patterns exposed at different exposure amounts was observed using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.) at a magnification of 200k. The minimum dot width that did not cause pattern collapse was found within one observed field of view and used as an indicator of pattern collapse. The smaller the value, the better the pattern collapse performance. The minimum dot width obtained was evaluated using the following evaluation criteria. In addition, in actual use, "C" evaluation or above is preferred. (Evaluation criteria) "A": Minimum dot width is less than 16nm "B": Minimum dot width is more than 16nm and less than 18nm "C": Minimum dot width is more than 18nm and less than 20nm "D": Minimum dot width is more than 20nm and less than 22nm "E": Minimum dot width is more than 22nm

Tables 1 to 12 are shown below. Below, the composition of each treatment liquid is shown in Table 1, Table 3, Table 5, Table 7, Table 9 and Table 11. In addition, Table 2, Table 4, Table 6, Table 8, Table 10 and Table 12 are respectively equivalent to the evaluation results of the patterns formed using the treatment liquids of Table 1, Table 3, Table 5, Table 7, Table 9 and Table 11. Specifically, Table 2 shows the evaluation results of the patterns formed using the treatment liquid of Table 1, Table 4 shows the evaluation results of the patterns formed using the treatment liquid of Table 3, Table 6 shows the evaluation results of the patterns formed using the treatment liquid of Table 5, Table 8 shows the evaluation results of the patterns formed using the treatment liquid of Table 7, Table 10 shows the evaluation results of the patterns formed using the treatment liquid of Table 9, and Table 12 shows the evaluation results of the patterns formed using the treatment liquid of Table 11.

Next, each item shown in Table 1, Table 3, Table 5, Table 7, Table 9 and Table 11 is explained. The "SP value" in each table is a value calculated according to the Fedors method, and the unit is MPa ^1/2 . The calculation method of the "SP value" is as described above. "δd" in each table represents the dispersion term of the Hansen solubility parameter. "ΔP" and "ΔH" in each table are calculated by the following formula (1) and the following formula (2), respectively. Formula (1): ΔP = δp/(δd+δp+δh)×100 Formula (2): ΔH = δh/(δd+δp+δh)×100 δd: dispersion term of Hansen solubility parameter δp: polar term of Hansen solubility parameter δh: hydrogen bond term of Hansen solubility parameter The calculation method of Hansen solubility parameter is as described above.

[Table 1] Table 1 Treatment fluid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) Type CAS SP value ΔD ΔP ΔH Type CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment solution A-1 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 40 Treatment solution A-2 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 40 Treatment solution A-3 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 25 Treatment fluid A-4 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 7 3 15 Treatment fluid A-5 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-Ethyl-1-hexanol 104-76-6 20.7 66.3 14.6 19.1 2.8 7 3 30 Treatment fluid A-6 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 1-Heptanol 111-70-6 21.4 48.9 15.9 35.2 2.4 7 3 20 Treatment fluid A-7 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 45 Treatment fluid A-8 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 45 Treatment fluid A-9 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 5 5 45 Treatment fluid A-10 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 3 7 45 Treatment fluid A-11 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 9 1 25 Treatment fluid A-12 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 30 Treatment fluid A-13 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 5 5 35 Treatment fluid A-14 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 3 7 40 Treatment fluid A-15 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 9 1 20 Treatment fluid A-16 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid A-17 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 5 5 30 Treatment fluid A-18 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 3 7 35 Treatment fluid A-19 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 9 1 20 Treatment fluid A-20 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 25 Treatment fluid A-21 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 5 5 30 Treatment fluid A-22 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 3 7 35 Treatment fluid A-23 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 9 1 18 Example A-24 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 7 3 twenty three Example A-25 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 5 5 28 Example A-26 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 3 7 32 Example A-27 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 9 1 20 Example A-28 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 7 3 25 Example A-29 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 5 5 30 Example A-30 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 3 7 35 Embodiment A-31 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 1-Octanol 111-87-5 21.0 49.7 15.5 34.8 4.0 7 3 45

[Table 2] Table 1 Treatment fluid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) Type CAS SP value ΔD ΔP ΔH Type CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid A-32 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 9 1 25 Treatment fluid A-33 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 5 5 60 Treatment fluid A-34 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 3 7 90 Treatment fluid A-35 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 1 9 130 Treatment fluid A-36 Dipentyl ether 693-65-2 16.2 71.9 14.3 13.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 50 Treatment fluid A-37 Dibutyl ether 142-96-1 15.9 71.1 14.2 14.7 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 30 Treatment fluid A-38 Diisopropyl ether 108-20-3 14.6 70.2 14.9 14.9 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 15 Treatment fluid A-39 Dipentyl ether 544-01-4 15.6 76.8 12.1 11.1 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 1 9 45 Treatment fluid A-40 Dibutyl ether 142-96-1 15.9 71.1 14.2 14.7 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 45 Treatment fluid A-41 Dipentyl ether 693-65-2 16.2 71.9 14.3 13.8 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 45 Treatment fluid A-42 Diisopropyl ether 108-20-3 14.6 70.2 14.9 14.9 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 45 Treatment fluid A-43 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 18 Treatment fluid A-44 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 5 5 53 Treatment fluid A-45 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 3 7 83 Treatment fluid A-46 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 1 9 123 Treatment fluid A-47 Dibutyl ether 142-96-1 15.9 71.1 14.2 14.7 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 43 Treatment fluid A-48 Dipentyl ether 693-65-2 16.2 71.9 14.3 13.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 twenty three Treatment fluid A-49 Diisopropyl ether 108-20-3 14.6 70.2 14.9 14.9 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 8 Treatment fluid A-50 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 9 1 20 Treatment fluid A-51 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 5 5 60 Treatment fluid A-52 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 3 7 90 Treatment fluid A-53 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 1 9 130 Treatment fluid A-54 Dibutyl ether 142-96-1 15.9 71.1 14.2 14.7 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 50 Treatment fluid A-55 Dipentyl ether 693-65-2 16.2 71.9 14.3 13.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 30 Treatment fluid A-56 Diisopropyl ether 108-20-3 14.6 70.2 14.9 14.9 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 15 Treatment fluid A-57 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 9 1 15 Treatment fluid A-58 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 5 5 40 Treatment fluid A-59 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 3 7 60 Treatment fluid A-60 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 1 9 85 Treatment fluid A-61 Dibutyl ether 142-96-1 15.9 71.1 14.2 14.7 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 35 Treatment fluid A-62 Dipentyl ether 693-65-2 16.2 71.9 14.3 13.8 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 20

[table 3] Table 1 Treatment fluid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) Type CAS SP value ΔD ΔP ΔH Type CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid A-63 Diisopropyl ether 108-20-3 14.6 70.2 14.9 14.9 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 8 Treatment fluid A-64 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 9 1 20 Treatment fluid A-65 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 5 5 45 Treatment fluid A-66 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 3 7 65 Treatment fluid A-67 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 1 9 90 Treatment fluid A-68 Dibutyl ether 142-96-1 15.9 71.1 14.2 14.7 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 40 Example A-69 Dipentyl ether 693-65-2 16.2 71.9 14.3 13.8 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 25 Example A-70 Diisopropyl ether 108-20-3 14.6 70.2 14.9 14.9 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 10 Treatment liquid RA-1 Triethyl orthoformate 122-51-0 16.3 59.9 22.2 17.9 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 40 Treatment liquid RA-2 Diethylene glycol diethyl ether 112-36-7 15.5 60.4 19.6 20.0 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 40 Treatment fluid RA-3 Triethyl orthopropionate 115-80-0 16.2 66.5 18.7 14.8 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 40 Treatment fluid RA-4 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-Butanol 78-92-2 20.7 43.9 15.8 40.3 0.6 9 1 15 Treatment liquid RA-5 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 MIBC 108-11-2 21.1 51.5 14.5 34.0 1.5 9 1 20 Treatment fluid RA-6 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Benzyl alcohol 100-51-6 21.1 47.9 16.4 35.7 1.1 9 1 25

[Table 4] Table 2 Type of treatment fluid Evaluation results Resolution Exposure film damage Bridging Defect Resistivity Dense pattern DOT logo Sparse pattern Embodiment A-1 Treatment solution A-1 A B A A A A Embodiment A-2 Treatment solution A-2 A B A A A A Embodiment A-3 Treatment solution A-3 A B A A A A Embodiment A-4 Treatment fluid A-4 A A A A A C Embodiment A-5 Treatment fluid A-5 A B A A B A Embodiment A-6 Treatment fluid A-6 C C C C A A Embodiment A-7 Treatment fluid A-7 A B A A A A Embodiment A-8 Treatment fluid A-8 A B A A A A Embodiment A-9 Treatment fluid A-9 A C A A A A Embodiment A-10 Treatment fluid A-10 A C A A A A Embodiment A-11 Treatment fluid A-11 A A A A A A Example A-12 Treatment fluid A-12 A A A A A A Embodiment A-13 Treatment fluid A-13 A B A A A A Embodiment A-14 Treatment fluid A-14 A B A A A A Embodiment A-15 Treatment fluid A-15 A A A A A A Embodiment A-16 Treatment fluid A-16 A A A A A A Embodiment A-17 Treatment fluid A-17 A A A A A A Embodiment A-18 Treatment fluid A-18 A B A A A A Embodiment A-19 Treatment fluid A-19 A A A A A A Example A-20 Treatment fluid A-20 A B A A A A Embodiment A-21 Treatment fluid A-21 B B A A A A Example A-22 Treatment fluid A-22 C B B A A A Example A-23 Treatment fluid A-23 A A A A A A Example A-24 Example A-24 A A A A A A Example A-25 Example A-25 A A A A A A Example A-26 Example A-26 A B A A A A Example A-27 Example A-27 A A A A A A Example A-28 Example A-28 A A A A A A Example A-29 Example A-29 A B A A A A Example A-30 Example A-30 B B A A A A Embodiment A-31 Embodiment A-31 B C B B A A Example A-32 Treatment fluid A-32 A B A A B B Example A-33 Treatment fluid A-33 A B A A A A Example A-34 Treatment fluid A-34 A B A A A A Example A-35 Treatment fluid A-35 B C A A A A Example A-36 Treatment fluid A-36 C C B A A A Example A-37 Treatment fluid A-37 C C B A A A Example A-38 Treatment fluid A-38 B C B A A A Example A-39 Treatment fluid A-39 B B B A A A Example A-40 Treatment fluid A-40 B B A A A A

[table 5] Table 2 Type of treatment fluid Evaluation results Resolution Exposure film damage Bridging Defect Resistivity Dense pattern DOT logo Sparse pattern Example A-41 Treatment fluid A-41 B B A A A A Example A-42 Treatment fluid A-42 B B A A A A Example A-43 Treatment fluid A-43 A A A C B B Example A-44 Treatment fluid A-44 A A A C A A Example A-45 Treatment fluid A-45 A A A C A A Example A-46 Treatment fluid A-46 A A A C A A Example A-47 Treatment fluid A-47 A B A C A A Example A-48 Treatment fluid A-48 A B A C A A Example A-49 Treatment fluid A-49 A B A C A A Example A-50 Treatment fluid A-50 A B A A B B Embodiment A-51 Treatment fluid A-51 A B A A A A Example A-52 Treatment fluid A-52 B B A A A A Example A-53 Treatment fluid A-53 C C B A A A Example A-54 Treatment fluid A-54 C C B A A A Example A-55 Treatment fluid A-55 C C B A A A Example A-56 Treatment fluid A-56 B C B A A A Example A-57 Treatment fluid A-57 A B A A B A Example A-58 Treatment fluid A-58 A B A A A A Example A-59 Treatment fluid A-59 B C B A A A Example A-60 Treatment fluid A-60 B C B A A A Embodiment A-61 Treatment fluid A-61 B C B A A A Example A-62 Treatment fluid A-62 B C B A A A Example A-63 Treatment fluid A-63 B C B A A A Embodiment A-64 Treatment fluid A-64 A B A A B A Example A-65 Treatment fluid A-65 A B A A B A Example A-66 Treatment fluid A-66 B B A A A A Example A-67 Treatment fluid A-67 C C A A A A Example A-68 Treatment fluid A-68 C C B A A A Example A-69 Example A-69 C C B A A A Example A-70 Example A-70 B C B A A A Comparative Example A-1 Treatment liquid RA-1 E E D B A A Comparative Example A-2 Treatment liquid RA-2 E E E E A A Comparative Example A-3 Treatment fluid RA-3 E E D B A A Comparative Example A-4 Treatment fluid RA-4 E E E E A A Comparative Example A-5 Treatment liquid RA-5 E E E E A A Comparative Example A-6 Treatment fluid RA-6 E E E E A A

The results in Table 2 confirm that the processing solution of the embodiment (the processing solution containing an ether solvent as solvent A-1 and an alcohol solvent as solvent B-1) can form a pattern in which pattern collapse is suppressed, film loss in the exposed part is suppressed, and bridge defects are suppressed. In addition, it is confirmed that the processing solution of the embodiment has a low resistivity and excellent safety. Furthermore, the results in Table 2 confirm that when the second organic solvent includes one or more selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2,6-dimethyl-4-heptanol, 2-ethyl-1-hexanol and 2-octanol, or includes any one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or includes a non-cyclic alcohol solvent having a triple bond in the molecule (preferably one or more selected from 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol), pattern collapse is further suppressed, and film loss in the exposed portion is further suppressed. Furthermore, it was confirmed that when the second organic solvent includes one or more selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2,6-dimethyl-4-heptanol and 2-octanol, or includes one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or includes a non-cyclic alcohol solvent having a triple bond in the molecule (preferably one or more selected from 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol), pattern collapse is further suppressed, film loss in the exposed part is further suppressed, and bridge defects are further suppressed. Furthermore, the results in Table 2 demonstrate that when the ΔP of the first organic solvent is 13.5 or less and the ΔD is 73.0 or more (preferably diisoamyl ether), a pattern in which pattern collapse is further suppressed can be formed.

Furthermore, the results in Table 2 confirm that when the ΔP of the first organic solvent is less than 13.5 and the ΔD is greater than 73.0, the second organic solvent contains 3,7-dimethyl-3-octanol, and the content of the first organic solvent is 20 to 80 mass % relative to the total content of the first organic solvent and the second organic solvent, a pattern collapse can be further suppressed, film loss in the exposed portion can be suppressed, and bridging defects can be suppressed, and the resistivity of the processing liquid itself is also appropriate.

Furthermore, the results in Table 2 confirm that when the ΔP of the first organic solvent is less than 13.5 and the ΔD is greater than 73.0, the second organic solvent includes any one of 3,5,5-trimethyl-1-hexanol and 3-ethyl-3-pentanol, and the content of the first organic solvent is 40 to 80 mass % relative to the total content of the first organic solvent and the second organic solvent, a pattern collapse can be further suppressed, film loss in the exposed portion is suppressed, and bridging defects are suppressed, and the resistivity of the processing liquid itself is also appropriate.

Furthermore, the results in Table 2 confirm that when the second organic solvent contains 2,6-dimethyl-4-heptanol and the content of the first organic solvent is 80% by mass or less relative to the total content of the first organic solvent and the second organic solvent, a pattern in which pattern collapse is further suppressed and bridging defects are further suppressed can be formed. Furthermore, the results in Table 2 confirm that when the second organic solvent is 2-ethyl-1-hexanol and the content of the first organic solvent is 40% by mass or more relative to the total content of the first organic solvent and the second organic solvent, pattern collapse can be further suppressed. Furthermore, when the second organic solvent is 2-ethyl-1-hexanol and the content of the first organic solvent is less than 40 mass % relative to the total content of the first organic solvent and the second organic solvent, a pattern in which bridge defects are further suppressed can be formed.

Furthermore, the results in Table 2 confirm that when the ΔP of the first organic solvent is less than 13.5 and the ΔD is greater than 73.0, the second organic solvent contains 2-octanol, and the content of the first organic solvent is 20 to 80 mass % relative to the total content of the first organic solvent and the second organic solvent, a pattern in which pattern collapse is further suppressed, film loss in the exposed portion is further suppressed, and bridging defects are further suppressed can be formed.

It was confirmed that the treatment solution of the comparative example did not meet the desired requirements.

[Table 6] table 3 Treatment fluid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) Type CAS SP value ΔD ΔP ΔH Type CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment solution B-1 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Ethyl acetylacetate 141-97-9 20.7 51.4 22.7 25.9 0.3 7 3 30 Treatment solution B-2 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Dimethyl malonate 108-59-8 20.6 49.8 21.0 29.1 0.07 7 3 35 Treatment solution B-3 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Methyl pyruvate 600-22-6 21.6 47.1 28.4 24.5 -0.37 9 1 25 Treatment liquid B-4 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Ethyl pyruvate 617-35-6 21.1 49.6 27.2 23.3 0.16 9 1 25 Treatment liquid B-5 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Diethyl oxalate 95-92-1 21.8 49.1 24.2 26.7 0.89 9 1 25 Treatment fluid B-6 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Dimethyl malonate 108-59-8 20.6 49.8 21.0 29.1 0.07 9 1 25 Treatment fluid B-7 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Dimethyl malonate 108-59-8 20.6 49.8 21.0 29.1 0.07 3 7 45 Treatment fluid B-8 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Ethyl acetylacetate 141-97-9 20.7 51.4 22.7 25.9 0.3 9 1 20 Treatment fluid B-9 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Ethyl acetylacetate 141-97-9 20.7 51.4 22.7 25.9 0.3 3 7 40 Treatment fluid RB-1 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Propylene glycol-1-monomethyl ether-2-acetate 108-65-6 17.9 50.3 18.1 31.6 0.6 7 3 25 Treatment fluid RB-2 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-Ethoxyethyl acetate 111-15-9 18.2 58.0 20.3 21.7 0.7 7 3 25 Treatment fluid RB-3 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Methyl benzoate 93-58-3 21.1 59.4 25.8 14.8 2.11 7 3 40

[Table 7] Table 4 Type of treatment fluid Evaluation results Resolution Exposure film damage Bridging Defect Resistivity Dense pattern Sparse pattern Example B-1 Treatment solution B-1 C B B A A Example B-2 Treatment solution B-2 C B B A A Example B-3 Treatment solution B-3 B B A B A Example B-4 Treatment liquid B-4 B B A B A Example B-5 Treatment fluid B-5 B B A B A Example B-6 Treatment fluid B-6 B B A B A Example B-7 Treatment fluid B-7 C B C A A Example B-8 Treatment fluid B-8 B B A A A Example B-9 Treatment fluid B-9 C B C A A Comparative Example B-1 Treatment fluid RB-1 E E E A A Comparative Example B-2 Treatment fluid RB-2 E E E D A Comparative Example B-3 Treatment fluid RB-3 C B E D A

The results of Table 4 confirm that the treatment liquid according to the embodiment (the treatment liquid containing an ether solvent as solvent A-1 and an ester solvent as solvent B-2) can form a pattern in which pattern collapse is suppressed, film loss in the exposure part is suppressed, and bridge defects are suppressed. In addition, it is confirmed that the treatment liquid of the embodiment has a low resistivity and excellent safety. In addition, the results of Table 4 confirm that when the content of the first organic solvent is 50% by mass or more (preferably 80% by mass or more) relative to the total content of the first organic solvent and the second organic solvent, a pattern in which pattern collapse is further suppressed and film loss in the exposure part is further suppressed can be formed, and the resistivity of the treatment liquid itself is also appropriate. Among them, when the second organic solvent is ethyl acetylacetate and the content of the first organic solvent is 80 mass % or more relative to the total content of the first organic solvent and the second organic solvent, a pattern collapse can be further suppressed, film damage in the exposed part can be further suppressed, and bridging defects can be further suppressed, and the resistivity of the processing liquid itself is also appropriate.

It was confirmed that the treatment solution of the comparative example did not meet the desired requirements.

[Table 8] table 5 Treatment fluid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) Type CAS SP value ΔD ΔP ΔH Type CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment solution C-1 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 30 Treatment solution C-2 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 30 Treatment fluid C-3 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 7 3 10 Treatment fluid C-4 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 15 Treatment fluid C-5 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-Ethyl-1-hexanol 104-76-6 20.7 66.3 14.6 19.1 2.8 7 3 20 Treatment fluid C-6 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 9 1 15 Treatment fluid C-7 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 5 5 45 Treatment fluid C-8 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 3 7 75 Treatment fluid C-9 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 1 9 110 Treatment fluid C-10 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 15 Treatment fluid C-11 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 30 Treatment fluid C-12 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 5 5 45 Treatment fluid C-13 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 3 7 75 Treatment fluid C-14 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 1 9 110 Treatment fluid C-15 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 9 1 25 Treatment fluid C-16 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 30 Treatment fluid C-17 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 5 5 35 Treatment fluid C-18 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 3 7 40 Treatment fluid C-19 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 9 1 20 Treatment fluid C-20 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid C-21 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 5 5 30 Treatment fluid C-22 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 3 7 35 Treatment fluid C-23 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 9 1 20 Treatment fluid C-24 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 25 Treatment fluid C-25 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 5 5 30 Treatment fluid C-26 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 3 7 35 Treatment fluid C-27 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 9 1 20 Treatment fluid C-28 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 7 3 twenty four Treatment fluid C-29 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 5 5 28 Treatment fluid C-30 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 3 7 33

[Table 9] Table 5 Treatment fluid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) Type CAS SP value ΔD ΔP ΔH Type CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid C-31 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 9 1 twenty two Treatment fluid C-32 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 7 3 27 Treatment fluid C-33 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 5 5 33 Treatment fluid C-34 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 3 7 39 Treatment fluid C-35 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 9 1 15 Treatment fluid C-36 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 5 5 45 Treatment fluid C-37 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 3 7 75 Treatment fluid C-38 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 1 9 110 Treatment fluid C-39 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 13 Treatment fluid C-40 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 5 5 40 Treatment fluid C-41 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 3 7 70 Treatment fluid C-42 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 1 9 95 Treatment fluid C-43 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 9 1 10 Treatment fluid C-44 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 5 5 40 Treatment fluid C-45 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 3 7 60 Treatment fluid C-46 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 1 9 80 Treatment fluid C-47 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 9 1 10 Treatment fluid C-48 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 5 5 40 Treatment fluid C-49 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 3 7 60 Treatment fluid C-50 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 1 9 80 Treatment fluid C-51 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 45 Treatment fluid C-52 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 45 Treatment fluid C-53 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 30 Treatment fluid C-54 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 2-Ethyl-1-hexanol 104-76-7 20.7 63.3 14.6 19.1 2.8 7 3 35 Treatment fluid C-55 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 9 1 20 Treatment fluid C-56 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 5 5 50 Treatment fluid C-57 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 3 7 80 Treatment fluid C-58 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 1 9 115 Treatment fluid C-59 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 15 Treatment fluid C-60 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 30

[Table 10] Table 5 Treatment fluid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) Type CAS SP value ΔD ΔP ΔH Type CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid C-61 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 5 5 45 Treatment fluid C-62 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 3 7 75 Treatment fluid C-63 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 1 9 110 Treatment fluid C-64 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 9 1 25 Treatment fluid C-65 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 30 Treatment fluid C-66 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 5 5 35 Treatment fluid C-67 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 3 7 40 Treatment fluid C-68 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 9 1 20 Treatment fluid C-69 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid C-70 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 5 5 30 Treatment fluid C-71 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 3 7 35 Treatment fluid C-72 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 9 1 20 Treatment fluid C-73 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 25 Treatment fluid C-74 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 5 5 30 Treatment fluid C-75 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 3 7 35 Treatment fluid C-76 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 9 1 18 Treatment fluid C-77 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 7 3 twenty two Treatment fluid C-78 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 5 5 27 Treatment fluid C-79 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 3 7 32 Treatment fluid C-80 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 9 1 twenty two Treatment fluid C-81 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 7 3 27 Treatment fluid C-82 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 5 5 32 Treatment fluid C-83 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 3 7 38 Treatment fluid C-84 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 14 Treatment fluid C-85 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 7 3 35 Treatment fluid C-86 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 5 5 42 Treatment fluid C-87 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 3 7 70 Treatment fluid C-88 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 1 9 100 Treatment fluid C-89 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 9 1 20 Treatment fluid C-90 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 5 5 50

[Table 11] Table 5 Treatment fluid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) Type CAS SP value ΔD ΔP ΔH Type CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid C-91 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 3 7 80 Treatment fluid C-92 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 1 9 115 Treatment fluid C-93 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 9 1 15 Treatment fluid C-94 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 5 5 45 Treatment fluid C-95 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 3 7 65 Treatment fluid C-96 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 1 9 85 Treatment fluid C-97 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 9 1 15 Treatment fluid C-98 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 5 5 45 Treatment fluid C-99 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 3 7 65 Treatment fluid C-100 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 1 9 85 Treatment fluid C-101 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 35 Treatment fluid C-102 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 35 Treatment fluid C-103 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 20 Treatment fluid C-104 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 25 Treatment fluid C-105 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 9 1 20 Treatment fluid C-106 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 5 5 50 Treatment fluid C-107 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 3 7 80 Treatment fluid C-108 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 1 9 115 Treatment fluid C-109 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 15 Treatment fluid C-110 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 30 Treatment fluid C-111 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 5 5 45 Treatment fluid C-112 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 3 7 75 Treatment fluid C-113 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 1 9 110 Treatment fluid C-114 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 9 1 25 Treatment fluid C-115 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 30 Treatment fluid C-116 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 5 5 35 Treatment fluid C-117 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 3 7 40 Treatment fluid C-118 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 9 1 20 Treatment fluid C-119 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid C-120 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 5 5 30

[Table 12] Table 5 Treatment fluid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) Type CAS SP value ΔD ΔP ΔH Type CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid C-121 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 3 7 35 Treatment fluid C-122 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 9 1 20 Treatment fluid C-123 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 25 Treatment fluid C-124 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 5 5 30 Treatment fluid C-125 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 3 7 35 Treatment fluid C-126 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 14 Treatment fluid C-127 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 5 5 42 Treatment fluid C-128 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 3 7 70 Treatment fluid C-129 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 1 9 100 Treatment fluid C-130 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 9 1 20 Treatment fluid C-131 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 5 5 50 Treatment fluid C-132 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 3 7 80 Treatment fluid C-133 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 1 9 115 Treatment fluid C-134 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 9 1 15 Treatment fluid C-135 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 5 5 45 Treatment fluid C-136 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 3 7 65 Treatment fluid C-137 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 1 9 85 Treatment fluid C-138 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 9 1 15 Treatment fluid C-139 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 5 5 45 Treatment fluid C-140 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 3 7 65 Treatment fluid C-141 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 1 9 85 Treatment fluid C-142 Undecane 1120-21-4 15.9 100.0 0.0 0.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 55 Treatment fluid C-143 Undecane 1120-21-4 15.9 100.0 0.0 0.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 55 Treatment fluid C-144 Undecane 1120-21-4 15.9 100.0 0.0 0.0 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 30 Treatment fluid C-145 Undecane 1120-21-4 15.9 100.0 0.0 0.0 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid C-146 Undecane 1120-21-4 15.9 100.0 0.0 0.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 25 Treatment fluid C-147 Undecane 1120-21-4 15.9 100.0 0.0 0.0 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 30 Treatment fluid C-148 Undecane 1120-21-4 15.9 100.0 0.0 0.0 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 35 Treatment fluid RC-1 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-Butanol 78-92-2 20.7 43.9 15.8 40.3 0.6 9 1 15 Treatment fluid RC-2 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 MIBC 108-11-2 21.1 51.5 14.5 34.0 1.5 9 1 20 Treatment fluid RC-3 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Benzyl alcohol 100-51-6 21.1 47.9 16.4 35.7 1.1 9 1 25

[Table 13] Table 6 Type of treatment fluid Evaluation results Resolution Exposure film damage Bridging Defect Resistivity Dense pattern DOT logo Sparse pattern Example C-1 Treatment solution C-1 A B A A A B Example C-2 Treatment solution C-2 A B A A A B Example C-3 Treatment fluid C-3 A A A A A C Example C-4 Treatment fluid C-4 A B A A A A Example C-5 Treatment fluid C-5 A B A A B A Example C-6 Treatment fluid C-6 A B A A A B Example C-7 Treatment fluid C-7 A B A A A B Example C-8 Treatment fluid C-8 B B A A A B Example C-9 Treatment fluid C-9 B C A A A A Example C-10 Treatment fluid C-10 A B A A A B Example C-11 Treatment fluid C-11 A B A A A B Example C-12 Treatment fluid C-12 A B A A A B Example C-13 Treatment fluid C-13 A C A A A B Example C-14 Treatment fluid C-14 B C A A A A Example C-15 Treatment fluid C-15 A A A A A B Example C-16 Treatment fluid C-16 A A A A A A Example C-17 Treatment fluid C-17 A A A A A A Example C-18 Treatment fluid C-18 A B A A A A Example C-19 Treatment fluid C-19 A A A A A B Example C-20 Treatment fluid C-20 A A A A A A Example C-21 Treatment fluid C-21 A A A A A A Example C-22 Treatment fluid C-22 A A A A A A Example C-23 Treatment fluid C-23 A A A A A B Example C-24 Treatment fluid C-24 A A A A A A Example C-25 Treatment fluid C-25 A B A A A A Example C-26 Treatment fluid C-26 B B A A A A Example C-27 Treatment fluid C-27 A A A A A B Example C-28 Treatment fluid C-28 A A A A A A Example C-29 Treatment fluid C-29 A A A A A A Example C-30 Treatment fluid C-30 A A A A A A Example C-31 Treatment fluid C-31 A A A A A B Example C-32 Treatment fluid C-32 A A A A A A Example C-33 Treatment fluid C-33 A A A A A A Example C-34 Treatment fluid C-34 B B A A A A Example C-35 Treatment fluid C-35 A B A A A C Example C-36 Treatment fluid C-36 A B A A A C Example C-37 Treatment fluid C-37 A C A A A C Example C-38 Treatment fluid C-38 A C B A A C Example C-39 Treatment fluid C-39 A A A A A C Example C-40 Treatment fluid C-40 A A A A A C Example C-41 Treatment fluid C-41 A A A A A C Example C-42 Treatment fluid C-42 A A A A A C Example C-43 Treatment fluid C-43 A B A A A B Example C-44 Treatment fluid C-44 A B A A A A Example C-45 Treatment fluid C-45 A B A A A A

[Table 14] Table 6 Type of treatment fluid Evaluation results Resolution Exposure film damage Bridging Defect Resistivity Dense pattern DOT logo Sparse pattern Example C-46 Treatment fluid C-46 A B B A A A Example C-47 Treatment fluid C-47 A B A A B B Example C-48 Treatment fluid C-48 A B A A B A Example C-49 Treatment fluid C-49 A B A A A A Example C-50 Treatment fluid C-50 A C A A A A Example C-51 Treatment fluid C-51 A B A A A B Example C-52 Treatment fluid C-52 A B A A A B Example C-53 Treatment fluid C-53 A B A A A A Example C-54 Treatment fluid C-54 A B A A B A Example C-55 Treatment fluid C-55 A B A A A B Example C-56 Treatment fluid C-56 B B A A A B Example C-57 Treatment fluid C-57 C B A A A B Example C-58 Treatment fluid C-58 C B A A A A Example C-59 Treatment fluid C-59 A C A A A B Example C-60 Treatment fluid C-60 A B A A A B Example C-61 Treatment fluid C-61 A B A A A B Example C-62 Treatment fluid C-62 A C A A A A Example C-63 Treatment fluid C-63 B C A A A A Example C-64 Treatment fluid C-64 A A A A A B Example C-65 Treatment fluid C-65 A A A A A A Example C-66 Treatment fluid C-66 A A A A A A Example C-67 Treatment fluid C-67 A B A A A A Example C-68 Treatment fluid C-68 A A A A A B Example C-69 Treatment fluid C-69 A A A A A A Example C-70 Treatment fluid C-70 A A A A A A Example C-71 Treatment fluid C-71 A A A A A A Example C-72 Treatment fluid C-72 A A A A A B Example C-73 Treatment fluid C-73 A A A A A A Example C-74 Treatment fluid C-74 A B A A A A Example C-75 Treatment fluid C-75 B B A A A A Example C-76 Treatment fluid C-76 A A A A A B Example C-77 Treatment fluid C-77 A A A A A A Example C-78 Treatment fluid C-78 A A A A A A Example C-79 Treatment fluid C-79 A A A A A A Example C-80 Treatment fluid C-80 A A A A A B Example C-81 Treatment fluid C-81 A A A A A A Example C-82 Treatment fluid C-82 A A A A A A Example C-83 Treatment fluid C-83 B B A A A A Example C-84 Treatment fluid C-84 A A A A A B Example C-85 Treatment fluid C-85 A A A A A B Example C-86 Treatment fluid C-86 A A A A A B Example C-87 Treatment fluid C-87 A A A A A C Example C-88 Treatment fluid C-88 A A A A A C Example C-89 Treatment fluid C-89 A B A A A B Example C-90 Treatment fluid C-90 A B A A A B

[Table 15] Table 6 Type of treatment fluid Evaluation results Resolution Exposure film damage Bridging Defect Resistivity Dense pattern DOT logo Sparse pattern Example C-91 Treatment fluid C-91 B C A A A B Example C-92 Treatment fluid C-92 B C B A A A Example C-93 Treatment fluid C-93 A B A A A B Example C-94 Treatment fluid C-94 A B A A A A Example C-95 Treatment fluid C-95 B C A A A A Example C-96 Treatment fluid C-96 B C B A A A Example C-97 Treatment fluid C-97 A B A A B B Example C-98 Treatment fluid C-98 A B A A B A Example C-99 Treatment fluid C-99 B C A A A A Example C-100 Treatment fluid C-100 C C A A A A Example C-101 Treatment fluid C-101 A B A A A B Example C-102 Treatment fluid C-102 A B A A A B Example C-103 Treatment fluid C-103 A B A A A A Example C-104 Treatment fluid C-104 A B A A B A Example C-105 Treatment fluid C-105 A B A A A B Example C-106 Treatment fluid C-106 A B A A A B Example C-107 Treatment fluid C-107 B B A A A B Example C-108 Treatment fluid C-108 B C A A A A Example C-109 Treatment fluid C-109 A B A A A B Example C-110 Treatment fluid C-110 A B A A A B Example C-111 Treatment fluid C-111 A B A A A B Example C-112 Treatment fluid C-112 A C A A A A Example C-113 Treatment fluid C-113 B C A A A A Example C-114 Treatment fluid C-114 A A A A A B Example C-115 Treatment fluid C-115 A A A A A A Example C-116 Treatment fluid C-116 A A A A A A Example C-117 Treatment fluid C-117 A B A A A A Example C-118 Treatment fluid C-118 A A A A A B Example C-119 Treatment fluid C-119 A A A A A A Example C-120 Treatment fluid C-120 A A A A A A Example C-121 Treatment fluid C-121 A A A A A A Example C-122 Treatment fluid C-122 A A A A A B Example C-123 Treatment fluid C-123 A A A A A A Example C-124 Treatment fluid C-124 A B A A A A Example C-125 Treatment fluid C-125 B B A A A A Example C-126 Treatment fluid C-126 A A A A A B Example C-127 Treatment fluid C-127 A A A A A B Example C-128 Treatment fluid C-128 A A A A A C Example C-129 Treatment fluid C-129 A A A A A C Example C-130 Treatment fluid C-130 A B A A A B Example C-131 Treatment fluid C-131 A B A A A B Example C-132 Treatment fluid C-132 A C A A A B Example C-133 Treatment fluid C-133 A C B A A A Example C-134 Treatment fluid C-134 A B A A A B Example C-135 Treatment fluid C-135 A B A A A A Example C-136 Treatment fluid C-136 A C A A A A

[Table 16] Table 6 Type of treatment fluid Evaluation results Resolution Exposure film damage Bridging Defect Resistivity Dense pattern DOT logo Sparse pattern Example C-137 Treatment fluid C-137 A C B A A A Example C-138 Treatment fluid C-138 A B A A B B Example C-139 Treatment fluid C-139 A B A A B A Example C-140 Treatment fluid C-140 A C A A A A Example C-141 Treatment fluid C-141 A C A A A A Example C-142 Treatment fluid C-142 C B A A A B Example C-143 Treatment fluid C-143 C B A A A B Example C-144 Treatment fluid C-144 A A A A A A Example C-145 Treatment fluid C-145 A A A A A A Example C-146 Treatment fluid C-146 A A A A A A Example C-147 Treatment fluid C-147 B B A A A A Example C-148 Treatment fluid C-148 C B A A B A Comparison Example RC-1 Treatment fluid RC-1 E E E E A A Comparison Example RC-2 Treatment fluid RC-2 C D C E A A Comparison Example RC-3 Treatment fluid RC-3 D E D E A A

The results in Table 6 confirm that the processing solution according to the embodiment (the processing solution containing a hydrocarbon solvent as solvent A-1 and an alcohol solvent as solvent B-1) can form a pattern in which pattern collapse is suppressed, film loss in the exposed part is suppressed, and bridge defects are suppressed. Furthermore, the results in Table 6 confirm that when the second organic solvent includes one or more selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2,6-dimethyl-4-heptanol and 2-octanol, or includes any one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or includes a non-cyclic alcohol solvent having a triple bond in the molecule (preferably one or more selected from 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol), pattern collapse is further suppressed, film loss in the exposed portion is further suppressed, and bridging defects are further suppressed. Among them, it was confirmed that when the second organic solvent includes one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or includes a non-cyclic alcohol solvent having a triple bond in the molecule (preferably one or more selected from 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol), regardless of the type of the first organic solvent and the content ratio of the first organic solvent to the second organic solvent, pattern collapse is further suppressed, film loss in the exposed part is further suppressed, and bridging defects are further suppressed. Furthermore, the results in Table 6 confirm that when the second organic solvent contains 3,7-dimethyl-3-octanol and the content of the first organic solvent is 40-80 mass % (preferably 60-80 mass %) relative to the total content of the first organic solvent and the second organic solvent, a pattern collapse can be further suppressed, film loss in the exposed part can be further suppressed, and bridging defects can be further suppressed. Furthermore, the results in Table 6 confirm that when the second organic solvent contains one or more selected from 3,5,5-trimethyl-1-hexanol and 3-ethyl-3-pentanol, and the content of the first organic solvent is 20 to 80 mass % (preferably 40 to 80 mass %) relative to the total content of the first organic solvent and the second organic solvent, a pattern collapse can be further suppressed, film loss in the exposure part can be further suppressed, and bridging defects can be further suppressed. Furthermore, the results in Table 6 confirm that when the second organic solvent contains 2-octanol and the content of the first organic solvent is 20 to 80 mass % relative to the total content of the first organic solvent and the second organic solvent, a pattern in which pattern collapse is further suppressed, film loss in the exposed portion is further suppressed, and bridging defects are further suppressed can be formed.

Furthermore, the results in Table 6 confirmed that when the second organic solvent is 2-ethyl-1-hexanol and the content of the first organic solvent is less than 40% by mass relative to the total content of the first organic solvent and the second organic solvent, a pattern in which pattern collapse is further suppressed, film loss in the exposed portion is further suppressed, and bridging defects are further suppressed can be formed. In particular, it was confirmed that when the first organic solvent contains 1,5-cyclooctadiene, the second organic solvent is 2-ethyl-1-hexanol, and the content of the first organic solvent is less than 40% by mass relative to the total content of the first organic solvent and the second organic solvent, a pattern in which pattern collapse is further suppressed, film loss in the exposed portion is further suppressed, and bridging defects are further suppressed can be formed.

It was confirmed that the treatment solution of the comparative example did not meet the desired requirements.

[Table 17] Table 7 Treatment fluid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) Type CAS SP value ΔD ΔP ΔH Type CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment solution D-1 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Ethyl acetylacetate 141-97-9 20.7 51.4 22.7 25.9 0.3 7 3 30 Treatment liquid D-2 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Dimethyl malonate 108-59-8 20.6 49.8 21.0 29.1 0.07 7 3 35 Treatment liquid D-3 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Methyl pyruvate 600-22-6 21.6 47.1 28.4 24.5 -0.37 9 1 20 Treatment liquid D-4 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Ethyl pyruvate 617-35-6 21.1 49.6 27.2 23.3 0.16 9 1 20 Treatment liquid D-5 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Diethyl oxalate 95-92-1 21.8 49.1 24.2 26.7 0.89 9 1 20 Treatment liquid D-6 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Dimethyl malonate 108-59-8 20.6 49.8 21.0 29.1 0.07 9 1 25 Treatment fluid D-7 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Dimethyl malonate 108-59-8 20.6 49.8 21.0 29.1 0.07 3 7 45 Treatment fluid D-8 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Ethyl acetylacetate 141-97-9 20.7 51.4 22.7 25.9 0.3 9 1 20 Treatment fluid D-9 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Ethyl acetylacetate 141-97-9 20.7 51.4 22.7 25.9 0.3 3 7 40 Treatment liquid D-10 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 Ethyl acetylacetate 141-97-9 20.7 51.4 22.7 25.9 0.3 7 3 30 Treatment liquid D-11 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 Dimethyl malonate 108-59-8 20.6 49.8 21.0 29.1 0.07 7 3 35 Treatment liquid D-12 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 Methyl pyruvate 600-22-6 21.6 47.1 28.4 24.5 -0.37 9 1 20 Treatment fluid D-13 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 Ethyl pyruvate 617-35-6 21.1 49.6 27.2 23.3 0.16 9 1 20 Treatment fluid D-14 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 Diethyl oxalate 95-92-1 21.8 49.1 24.2 26.7 0.89 9 1 20 Treatment liquid D-15 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 Dimethyl malonate 108-59-8 20.6 49.8 21.0 29.1 0.07 9 1 25 Treatment fluid D-16 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 Dimethyl malonate 108-59-8 20.6 49.8 21.0 29.1 0.07 3 7 45 Treatment fluid D-17 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 Ethyl acetylacetate 141-97-9 20.7 51.4 22.7 25.9 0.3 9 1 20 Treatment fluid D-18 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 Ethyl acetylacetate 141-97-9 20.7 51.4 22.7 25.9 0.3 3 7 40 Treatment fluid RD-1 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Propylene glycol-1-monomethyl ether-2-acetate 108-65-6 17.9 50.3 18.1 31.6 0.6 7 3 25.0 Treatment fluid RD-2 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-Ethoxyethyl acetate 111-15-9 18.2 58.0 20.3 21.7 0.7 7 3 25.0 Treatment fluid RD-3 Ethylcyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Methyl benzoate 93-58-3 21.1 59.4 25.8 14.8 2.11 7 3 40 Treatment fluid RD-4 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 Propylene glycol-1-monomethyl ether-2-acetate 108-65-6 17.9 50.3 18.1 31.6 0.6 7 3 25.0 Treatment fluid RD-5 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 2-Ethoxyethyl acetate 111-15-9 18.2 58.0 20.3 21.7 0.7 7 3 25.0 Treatment fluid RD-6 Symmetric trimethylol 108-67-8 18.6 93.8 3.1 3.1 Methyl benzoate 93-58-3 21.1 59.4 25.8 14.8 2.11 7 3 40

[Table 18] Table 8 Type of treatment fluid Evaluation results Resolution Exposure film damage Bridging Defect Resistivity Dense pattern Sparse pattern Embodiment D-1 Treatment solution D-1 C B B A A Example D-2 Treatment liquid D-2 C B B A A Embodiment D-3 Treatment liquid D-3 B B A B A Embodiment D-4 Treatment liquid D-4 B B A B A Embodiment D-5 Treatment liquid D-5 B B A B A Embodiment D-6 Treatment liquid D-6 B B A B A Embodiment D-7 Treatment fluid D-7 C B C A A Embodiment D-8 Treatment liquid D-8 B B A A A Example D-9 Treatment fluid D-9 C B C A A Embodiment D-10 Treatment liquid D-10 C B B A A Example D-11 Treatment liquid D-11 C B B A A Example D-12 Treatment liquid D-12 B B A B A Example D-13 Treatment fluid D-13 B B A B A Example D-14 Treatment fluid D-14 B B A B A Example D-15 Treatment liquid D-15 B B A B A Example D-16 Treatment fluid D-16 C B C A A Example D-17 Treatment fluid D-17 B B A A A Example D-18 Treatment fluid D-18 C B C A A Comparison Example RD-1 Treatment fluid RD-1 E E E A A Comparison Example RD-2 Treatment fluid RD-2 E E E D A Comparison Example RD-3 Treatment fluid RD-3 C B D D A Comparison Example RD-4 Treatment fluid RD-4 E E E A A Comparison Example RD-5 Treatment fluid RD-5 E E E D A Comparative Example RD-6 Treatment fluid RD-6 C B D D A

The results of Table 8 confirm that the processing liquid according to the embodiment (the processing liquid containing a hydrocarbon solvent as solvent A-1 and an ester solvent as solvent B-2) can form a pattern in which pattern collapse is suppressed, film loss in the exposure part is suppressed, and bridge defects are suppressed. In addition, it is confirmed that the processing liquid of the embodiment has a low resistivity and excellent safety. In addition, the results of Table 8 confirm that when the content of the first organic solvent is 50% by mass or more (preferably 80% by mass or more) relative to the total content of the first organic solvent and the second organic solvent, a pattern in which pattern collapse is further suppressed and film loss in the exposure part is further suppressed can be formed, and the resistivity of the processing liquid itself is also appropriate. Moreover, when the second organic solvent is ethyl acetylacetate and the content of the first organic solvent is 80 mass % or more relative to the total content of the first organic solvent and the second organic solvent, a pattern collapse can be further suppressed, film loss in the exposure portion can be further suppressed, and bridging defects can be further suppressed, and the resistivity of the processing liquid itself is also appropriate.

It was confirmed that the treatment solution of the comparative example did not meet the desired requirements.

[Table 19] Table 9 Treatment fluid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) Type CAS SP value ΔD ΔP ΔH Type CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid E-1 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 30 Treatment fluid E-2 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 30 Treatment fluid E-3 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 15 Treatment fluid E-4 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 20 Treatment fluid E-5 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 9 1 15 Treatment fluid E-6 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 5 5 45 Treatment fluid E-7 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 3 7 75 Treatment fluid E-8 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 1 9 110 Treatment fluid E-9 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 15 Treatment fluid E-10 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 30 Treatment fluid E-11 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 5 5 40 Treatment fluid E-12 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 3 7 65 Treatment fluid E-13 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 1 9 90 Treatment fluid E-14 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 9 1 25 Treatment fluid E-15 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 30 Treatment fluid E-16 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 5 5 35 Treatment fluid E-17 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 3 7 40 Treatment fluid E-18 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 1 9 45 Treatment fluid E-19 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 9 1 20 Treatment fluid E-20 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid E-21 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 5 5 30 Treatment fluid E-22 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 3 7 35 Treatment fluid E-23 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 1 9 40 Treatment fluid E-24 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 9 1 20 Treatment fluid E-25 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 25 Treatment fluid E-26 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 5 5 30 Treatment fluid E-27 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 3 7 35 Treatment fluid E-28 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 1 9 40 Treatment fluid E-29 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 9 1 18 Treatment fluid E-30 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 7 3 twenty two Treatment fluid E-31 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 5 5 28 Treatment fluid E-32 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 3 7 31 Treatment fluid E-33 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 1 9 35

[Table 20] Table 9 Treatment fluid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) Type CAS SP value ΔD ΔP ΔH Type CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid E-34 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 9 1 twenty two Treatment fluid E-35 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 7 3 28 Treatment fluid E-36 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 5 5 34 Treatment fluid E-37 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 3 7 40 Treatment fluid E-38 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 1 9 46 Treatment fluid E-39 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 15 Treatment fluid E-40 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 5 5 30 Treatment fluid E-41 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 5 5 40 Treatment fluid E-42 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 3 7 60 Treatment fluid E-43 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 1 9 85 Treatment fluid E-44 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 9 1 15 Treatment fluid E-45 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 5 5 45 Treatment fluid E-46 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 3 7 75 Treatment fluid E-47 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 1 9 110 Treatment fluid E-48 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 9 1 10 Treatment fluid E-49 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 5 5 40 Treatment fluid E-50 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 3 7 60 Treatment fluid E-51 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 1 9 80 Treatment fluid E-52 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 9 1 10 Treatment fluid E-53 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 5 5 40 Treatment fluid E-54 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 3 7 60 Treatment fluid E-55 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 1 9 80 Treatment fluid E-56 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 30 Treatment fluid E-57 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 30 Treatment fluid E-58 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 15 Treatment fluid E-59 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 20 Treatment fluid E-60 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 9 1 15 Treatment fluid E-61 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 5 5 45 Treatment fluid E-62 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 3 7 75 Treatment fluid E-63 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 1 9 110 Treatment fluid E-64 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 15 Treatment fluid E-65 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 30 Treatment fluid E-66 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 5 5 40 Treatment fluid E-67 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 3 7 65 Treatment fluid E-68 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 1 9 90

[Table 21] Table 9 Treatment fluid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) Type CAS SP value ΔD ΔP ΔH Type CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid E-69 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 9 1 25 Treatment fluid E-70 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 30 Treatment fluid E-71 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 5 5 35 Treatment fluid E-72 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 3 7 40 Treatment fluid E-73 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 1 9 45 Treatment fluid E-74 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 9 1 20 Treatment fluid E-75 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid E-76 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 5 5 30 Treatment fluid E-77 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 3 7 35 Treatment fluid E-78 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 1 9 40 Treatment fluid E-79 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 9 1 20 Treatment fluid E-80 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 25 Treatment fluid E-81 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 5 5 30 Treatment fluid E-82 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 3 7 35 Treatment fluid E-83 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 1 9 40 Treatment fluid E-84 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 9 1 19 Treatment fluid E-85 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 7 3 twenty three Treatment fluid E-86 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 5 5 30 Treatment fluid E-87 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 3 7 35 Treatment fluid E-88 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 1 9 41 Treatment fluid E-89 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 9 1 twenty four Treatment fluid E-90 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 7 3 30 Treatment fluid E-91 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 5 5 35 Treatment fluid E-92 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 3 7 40 Treatment fluid E-93 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 1 9 45 Treatment fluid E-94 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 15 Treatment fluid E-95 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 5 5 30 Treatment fluid E-96 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 5 5 40 Treatment fluid E-97 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 3 7 60 Treatment fluid E-98 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 1 9 85 Treatment fluid E-99 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 9 1 15 Treatment fluid E-100 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 5 5 45 Treatment fluid E-101 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 3 7 75 Treatment fluid E-102 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 1 9 110

[Table 22] Table 9 Treatment fluid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) Type CAS SP value ΔD ΔP ΔH Type CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid E-103 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 9 1 10 Treatment fluid E-104 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 5 5 40 Treatment fluid E-105 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 3 7 60 Treatment fluid E-106 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 1 9 80 Treatment fluid E-107 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 9 1 10 Treatment fluid E-108 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 5 5 40 Treatment fluid E-109 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 3 7 60 Treatment fluid E-110 Butyl butyrate 109-21-7 17.8 64.7 12.0 23.2 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 1 9 80 Treatment fluid E-111 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 30 Treatment fluid E-112 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 30 Treatment fluid E-113 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 15 Treatment fluid E-114 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 20 Treatment fluid E-115 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 9 1 15 Treatment fluid E-116 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 5 5 45 Treatment fluid E-117 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 3 7 75 Treatment fluid E-118 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 1 9 110 Treatment fluid E-119 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 15 Treatment fluid E-120 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 30 Treatment fluid E-121 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 5 5 40 Treatment fluid E-122 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 3 7 65 Treatment fluid E-123 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 1 9 90 Treatment fluid E-124 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 9 1 25 Treatment fluid E-125 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 30 Treatment fluid E-126 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 5 5 35 Treatment fluid E-127 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 3 7 40 Treatment fluid E-128 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 1 9 45 Treatment fluid E-129 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 9 1 20 Treatment fluid E-130 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid E-131 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 5 5 30 Treatment fluid E-132 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 3 7 35 Treatment fluid E-133 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 1 9 40 Treatment fluid E-134 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 9 1 20 Treatment fluid E-135 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 25 Treatment fluid E-136 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 5 5 30 Treatment fluid E-137 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 3 7 35 Treatment fluid E-138 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 1 9 40

[Table 23] Table 9 Treatment fluid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) Type CAS SP value ΔD ΔP ΔH Type CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid E-139 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 15 Treatment fluid E-140 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 7 3 30 Treatment fluid E-141 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 5 5 40 Treatment fluid E-142 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 3 7 60 Treatment fluid E-143 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 1 9 85 Treatment fluid E-144 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 9 1 15 Treatment fluid E-145 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 5 5 45 Treatment fluid E-146 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 3 7 75 Treatment fluid E-147 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 1 9 110 Treatment fluid E-148 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 9 1 10 Treatment fluid E-149 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 5 5 40 Treatment fluid E-150 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 3 7 60 Treatment fluid E-151 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 1 9 80 Treatment fluid E-152 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 9 1 10 Treatment fluid E-153 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 5 5 40 Treatment fluid E-154 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 3 7 60 Treatment fluid E-155 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 1 9 80 Treatment fluid E-156 Hexyl acetate 142-92-7 17.8 64.2 11.8 24.0 3,7-Dimethyl-3-octanol 78-69-6 19.7 65.7 10.3 24.0 3.5 7 3 55 Treatment fluid E-157 Hexyl acetate 142-92-7 17.8 64.2 11.8 24.0 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 30 Treatment fluid E-158 Hexyl acetate 142-92-7 17.8 64.2 11.8 24.0 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 30 Treatment fluid E-159 Hexyl acetate 142-92-7 17.8 64.2 11.8 24.0 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid E-160 Hexyl acetate 142-92-7 17.8 64.2 11.8 24.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 25 Treatment fluid E-161 Hexyl acetate 142-92-7 17.8 64.2 11.8 24.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 7 3 35 Treatment fluid E-162 Hexyl acetate 142-92-7 17.8 64.2 11.8 24.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 55 Treatment fluid E-163 Hexyl acetate 142-92-7 17.8 64.2 11.8 24.0 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 30 Treatment fluid E-164 Hexyl acetate 142-92-7 17.8 64.2 11.8 24.0 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 35 Treatment fluid RE-1 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-Butanol 78-92-2 20.7 43.9 15.8 40.3 0.6 9 1 15 Treatment fluid RE-2 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 4-Methyl-2-pentanol 108-11-2 21.1 51.5 14.5 34.0 1.5 9 1 20 Treatment fluid RE-3 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 Benzyl alcohol 100-51-6 21.1 47.9 16.4 35.7 1.1 9 1 25 Treatment fluid RE-4 Butyl crotonate 7299-91-4 19.9 63.4 15.2 21.4 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 13.0 24.0 3.5 7 3 55 Treatment fluid RE-5 Butyl crotonate 7299-91-4 19.9 63.4 15.2 21.4 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 30

[Table 24] Table 10 Type of treatment fluid Evaluation results Resolution Exposure film damage Bridging Defect Resistivity Dense pattern DOT logo Sparse pattern Embodiment E-1 Treatment fluid E-1 B C B A A A Embodiment E-2 Treatment fluid E-2 B C B A A A Embodiment E-3 Treatment fluid E-3 B C B A A A Embodiment E-4 Treatment fluid E-4 B C B A B A Embodiment E-5 Treatment fluid E-5 B B B A A A Embodiment E-6 Treatment fluid E-6 B C B A A A Embodiment E-7 Treatment fluid E-7 C C B A A A Embodiment E-8 Treatment fluid E-8 C C B A A A Embodiment E-9 Treatment fluid E-9 A B A A A A Embodiment E-10 Treatment fluid E-10 A B A A A A Embodiment E-11 Treatment fluid E-11 A B A A A A Embodiment E-12 Treatment fluid E-12 A C A A A A Embodiment E-13 Treatment fluid E-13 A C A A A A Embodiment E-14 Treatment fluid E-14 A A A A A A Embodiment E-15 Treatment fluid E-15 A A A A A A Embodiment E-16 Treatment fluid E-16 A A A A A A Embodiment E-17 Treatment fluid E-17 A A A A A A Embodiment E-18 Treatment fluid E-18 B A A A A A Embodiment E-19 Treatment fluid E-19 A B A A A A Embodiment E-20 Treatment fluid E-20 A A A A A A Embodiment E-21 Treatment fluid E-21 A A A A A A Example E-22 Treatment fluid E-22 A A A A A A Embodiment E-23 Treatment fluid E-23 A A A A A A Example E-24 Treatment fluid E-24 A A A A A A Example E-25 Treatment fluid E-25 A A A A A A Embodiment E-26 Treatment fluid E-26 A B A A A A Embodiment E-27 Treatment fluid E-27 A B A A A A Embodiment E-28 Treatment fluid E-28 A B A A A A Embodiment E-29 Treatment fluid E-29 A A A A A A Embodiment E-30 Treatment fluid E-30 A A A A A A Embodiment E-31 Treatment fluid E-31 A A A A A A Embodiment E-32 Treatment fluid E-32 A A A A A A Embodiment E-33 Treatment fluid E-33 A A A A A A Embodiment E-34 Treatment fluid E-34 A A A A A A Embodiment E-35 Treatment fluid E-35 A A A A A A Embodiment E-36 Treatment fluid E-36 A B A A A A Embodiment E-37 Treatment fluid E-37 A B A A A A Embodiment E-38 Treatment fluid E-38 A B A A A A Embodiment E-39 Treatment fluid E-39 A A A A A B Example E-40 Treatment fluid E-40 A A A A A B Embodiment E-41 Treatment fluid E-41 A A A A A B Embodiment E-42 Treatment fluid E-42 A A A A A B Embodiment E-43 Treatment fluid E-43 A A A A A B Embodiment E-44 Treatment fluid E-44 B B B A A A Example E-45 Treatment fluid E-45 B B B A A A

[Table 25] Table 10 Type of treatment fluid Evaluation results Resolution Exposure film damage Bridging Defect Resistivity Dense pattern DOT logo Sparse pattern Embodiment E-46 Treatment fluid E-46 B B B A A A Embodiment E-47 Treatment fluid E-47 B C C A A A Embodiment E-48 Treatment fluid E-48 B B B A A A Embodiment E-49 Treatment fluid E-49 B B B A A A Example E-50 Treatment fluid E-50 B C B A A A Embodiment E-51 Treatment fluid E-51 B C C A A A Embodiment E-52 Treatment fluid E-52 B B B A B A Embodiment E-53 Treatment fluid E-53 B B B A B A Embodiment E-54 Treatment fluid E-54 B C B A A A Embodiment E-55 Treatment fluid E-55 B C B A A A Embodiment E-56 Treatment fluid E-56 B B B A A A Embodiment E-57 Treatment fluid E-57 B B B A A A Embodiment E-58 Treatment fluid E-58 B B B A A A Embodiment E-59 Treatment fluid E-59 B B B A B A Example E-60 Treatment fluid E-60 B B B A A A Embodiment E-61 Treatment fluid E-61 B B B A A A Embodiment E-62 Treatment fluid E-62 C C B A A A Embodiment E-63 Treatment fluid E-63 C C B A A A Embodiment E-64 Treatment fluid E-64 A B A A A A Embodiment E-65 Treatment fluid E-65 A B A A A A Embodiment E-66 Treatment fluid E-66 A B A A A A Embodiment E-67 Treatment fluid E-67 A C A A A A Embodiment E-68 Treatment fluid E-68 A C A A A A Embodiment E-69 Treatment fluid E-69 A A A A A A Embodiment E-70 Treatment fluid E-70 A A A A A A Embodiment E-71 Treatment fluid E-71 A A A A A A Embodiment E-72 Treatment fluid E-72 A A A A A A Embodiment E-73 Treatment fluid E-73 A B A A A A Embodiment E-74 Treatment fluid E-74 A A A A A A Example E-75 Treatment fluid E-75 A A A A A A Embodiment E-76 Treatment fluid E-76 A A A A A A Embodiment E-77 Treatment fluid E-77 A A A A A A Embodiment E-78 Treatment fluid E-78 A A A A A A Embodiment E-79 Treatment fluid E-79 A A A A A A Example E-80 Treatment fluid E-80 A A A A A A Embodiment E-81 Treatment fluid E-81 A A A A A A Embodiment E-82 Treatment fluid E-82 A B A A A A Embodiment E-83 Treatment fluid E-83 A B A A A A Embodiment E-84 Treatment fluid E-84 A A A A A A Embodiment E-85 Treatment fluid E-85 A A A A A A Embodiment E-86 Treatment fluid E-86 A A A A A A Embodiment E-87 Treatment fluid E-87 A A A A A A Embodiment E-88 Treatment fluid E-88 A A A A A A Embodiment E-89 Treatment fluid E-89 A A A A A A Example E-90 Treatment fluid E-90 A A A A A A Embodiment E-91 Treatment fluid E-91 A A A A A A Embodiment E-92 Treatment fluid E-92 A B A A A A

[Table 26] Table 10 Type of treatment fluid Evaluation results Resolution Exposure film damage Bridging Defect Resistivity Dense pattern DOT logo Sparse pattern Embodiment E-93 Treatment fluid E-93 A B A A A A Embodiment E-94 Treatment fluid E-94 A A A A A B Embodiment E-95 Treatment fluid E-95 A A A A A B Embodiment E-96 Treatment fluid E-96 A A A A A B Embodiment E-97 Treatment fluid E-97 A A A A A B Embodiment E-98 Treatment fluid E-98 A A A A A B Embodiment E-99 Treatment fluid E-99 B B B A A A Example E-100 Treatment fluid E-100 B B B A A A Embodiment E-101 Treatment fluid E-101 B C B A A A Embodiment E-102 Treatment fluid E-102 B C C A A A Embodiment E-103 Treatment fluid E-103 B B B A A A Embodiment E-104 Treatment fluid E-104 B B B A A A Embodiment E-105 Treatment fluid E-105 B C B A A A Embodiment E-106 Treatment fluid E-106 B C C A A A Embodiment E-107 Treatment fluid E-107 B B B A B A Embodiment E-108 Treatment fluid E-108 B B B A B A Embodiment E-109 Treatment fluid E-109 B C B A A A Embodiment E-110 Treatment fluid E-110 B C B A A A Embodiment E-111 Treatment fluid E-111 B C B A A A Embodiment E-112 Treatment fluid E-112 B C B A A A Embodiment E-113 Treatment fluid E-113 B C B A A A Embodiment E-114 Treatment fluid E-114 B C B A B A Example E-115 Treatment fluid E-115 B C B A A A Example E-116 Treatment fluid E-116 B C B A A A Embodiment E-117 Treatment fluid E-117 C C B A A A Embodiment E-118 Treatment fluid E-118 C C B A A A Embodiment E-119 Treatment fluid E-119 A C A A A A Embodiment E-120 Treatment fluid E-120 A C A A A A Embodiment E-121 Treatment fluid E-121 A C A A A A Example E-122 Treatment fluid E-122 A C A A A A Example E-123 Treatment fluid E-123 A C A A A A Embodiment E-124 Treatment fluid E-124 A B A A A A Example E-125 Treatment fluid E-125 A B A A A A Example E-126 Treatment fluid E-126 A B A A A A Example E-127 Treatment fluid E-127 A B A A A A Embodiment E-128 Treatment fluid E-128 A C A A A A Embodiment E-129 Treatment fluid E-129 A B A A A A Embodiment E-130 Treatment fluid E-130 A B A A A A Embodiment E-131 Treatment fluid E-131 A B A A A A Example E-132 Treatment fluid E-132 A B A A A A Example E-133 Treatment fluid E-133 A C A A A A Embodiment E-134 Treatment fluid E-134 A B A A A A Example E-135 Treatment fluid E-135 A B A A A A Example E-136 Treatment fluid E-136 A C A A A A Example E-137 Treatment fluid E-137 A C A A A A Embodiment E-138 Treatment fluid E-138 A C A A A A

[Table 27] Table 10 Type of treatment fluid Evaluation results Resolution Exposure film damage Bridging Defect Resistivity Dense pattern DOT logo Sparse pattern Embodiment E-139 Treatment fluid E-139 A A A A A B Example E-140 Treatment fluid E-140 A A A A A B Embodiment E-141 Treatment fluid E-141 A B A A A B Example E-142 Treatment fluid E-142 A B A A A B Example E-143 Treatment fluid E-143 A B A A A B Embodiment E-144 Treatment fluid E-144 B C B A A A Example E-145 Treatment fluid E-145 B C B A A A Example E-146 Treatment fluid E-146 B C B A A A Embodiment E-147 Treatment fluid E-147 B C C A A A Embodiment E-148 Treatment fluid E-148 B C B A A A Example E-149 Treatment fluid E-149 B C B A A A Example E-150 Treatment fluid E-150 B C B A A A Embodiment E-151 Treatment fluid E-151 B C C A A A Example E-152 Treatment fluid E-152 B C B A B A Example E-153 Treatment fluid E-153 B C B A B A Example E-154 Treatment fluid E-154 B C B A A A Example E-155 Treatment fluid E-155 B C B A A A Example E-156 Treatment fluid E-156 C C B A A A Example E-157 Treatment fluid E-157 B C B A A A Embodiment E-158 Treatment fluid E-158 A B A A A A Embodiment E-159 Treatment fluid E-159 A B A A A A Embodiment E-160 Treatment fluid E-160 B B B A A A Embodiment E-161 Treatment fluid E-161 B B A A A C Example E-162 Treatment fluid E-162 C C B A A A Embodiment E-163 Treatment fluid E-163 C C B A A A Embodiment E-164 Treatment fluid E-164 C C B A B A Comparison Example RE-1 Treatment fluid RE-1 E E E E A A Comparison Example RE-2 Treatment fluid RE-2 D D D E A A Comparison Example RE-3 Treatment fluid RE-3 D E D E A A Comparison Example RE-4 Treatment fluid RE-4 E E E A A A Comparison Example RE-5 Treatment fluid RE-5 E E E A A A

The results in Table 10 confirm that the processing solution of the embodiment (the processing solution containing an ester solvent as solvent A-1 and an alcohol solvent as solvent B-1) can form a pattern in which pattern collapse is suppressed, film loss in the exposure part is suppressed, and bridge defects are suppressed. In addition, it is confirmed that the processing solution of the embodiment has a low resistivity and excellent safety. Furthermore, the results in Table 10 show that when the second organic solvent includes one or more selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol and 2-octanol, or includes one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or includes an alcohol solvent having a triple bond in the molecule (preferably one or more selected from 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol), pattern collapse is further suppressed, film loss in the exposed part is further suppressed, and bridge defects are further suppressed. Furthermore, it is confirmed that the resistivity of the treatment solution is low and the safety is excellent. Furthermore, it was confirmed that when the second organic solvent contained 2-octanol, any one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or a non-cyclic alcohol solvent having a triple bond in the molecule (preferably one or more selected from 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol), pattern collapse was further suppressed, film loss in the exposed portion was further suppressed, and bridging defects were further suppressed. Moreover, it was confirmed that when the second organic solvent includes any one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or includes a non-cyclic alcohol solvent having a triple bond in the molecule (preferably one or more selected from 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol), and the content of the first organic solvent is 60 mass % or more relative to the total content of the first organic solvent and the second organic solvent, pattern collapse is further suppressed, film loss in the exposed part is further suppressed, and bridging defects are further suppressed.

Furthermore, the results in Table 10 confirm that when the first organic solvent includes an organic solvent having an SP value of 18.7 MPa ^1/2 or less, ΔP of 15.0 or less, and ΔD of 64.5 or more, and the second organic solvent includes 3,7-dimethyl-3-octanol, and the content of the first organic solvent is 40 to 80 mass % relative to the total content of the first organic solvent and the second organic solvent, a pattern in which pattern collapse is further suppressed, film loss in the exposed portion is further suppressed, and bridging defects are further suppressed can be formed. Furthermore, the results in Table 10 demonstrate that when the first organic solvent includes an organic solvent having an SP value of 18.7 MPa ^1/2 or less, ΔP of 15.0 or less, and ΔD of 64.5 or more, and the second organic solvent includes one or more selected from 3,5,5-trimethyl-1-hexanol and 3-ethyl-3-pentanol, and the content of the first organic solvent is 20 to 80 mass % relative to the total content of the first organic solvent and the second organic solvent, a pattern in which pattern collapse is further suppressed, film loss in the exposed portion is further suppressed, and bridging defects are further suppressed can be formed.

Furthermore, the results in Table 10 demonstrate that when the first organic solvent includes an organic solvent having an SP value of 18.7 MPa ^1/2 or less, ΔP of 15.0 or less, and ΔD of 64.5 or more, and the second organic solvent includes one or more selected from 2-octanol or 2,6-dimethyl-4-heptanol, a pattern in which pattern collapse is further suppressed, film loss in the exposed portion is further suppressed, and bridging defects are further suppressed can be formed.

Furthermore, the results in Table 8 confirm that when the first organic solvent includes an organic solvent having an SP value of 18.7 MPa ^1/2 or less, ΔP of 15.0 or less, and ΔD of 64.5 or more, and the second organic solvent is 2-ethyl-1-hexanol, and the content of the first organic solvent is less than 40 mass % relative to the total content of the first organic solvent and the second organic solvent, a pattern in which pattern collapse is further suppressed, film loss in the exposure portion is further suppressed, and bridging defects are further suppressed can be formed.

Furthermore, the results in Table 10 confirm that when the first organic solvent is an organic solvent having a ΔD of 64.5 or more, the collapse of the formed pattern is further suppressed. For example, hexyl acetate, which is estimated to be an organic solvent having a ΔD of less than 64.5, has an ester functional group that is structurally easy to interact with the polymer at the end of the molecule, so it has higher polymer dispersibility and is easy to swell the resist compared to butyl butyrate of the same molecular formula.

It was confirmed that the treatment solution of the comparative example did not meet the desired requirements.

[Table 28] Table 11 Treatment fluid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) Type CAS SP value ΔD ΔP ΔH Type CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid F-1 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 30 Treatment fluid F-2 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 30 Treatment fluid F-3 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 15 Treatment fluid F-4 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 20 Treatment fluid F-5 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 7 3 15 Treatment fluid F-6 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 20 Treatment fluid F-7 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 12 Treatment fluid F-8 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 5 5 35 Treatment fluid F-9 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 3 7 55 Treatment fluid F-10 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 1 9 85 Treatment fluid F-11 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 15 Treatment fluid F-12 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 5 5 30 Treatment fluid F-13 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 3 7 60 Treatment fluid F-14 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 1 9 90 Treatment fluid F-15 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 9 1 10 Treatment fluid F-16 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 25 Treatment fluid F-17 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 5 5 30 Treatment fluid F-18 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 3 7 35 Treatment fluid F-19 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 1 9 40 Treatment fluid F-20 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 9 1 10 Treatment fluid F-21 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid F-22 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 5 5 30 Treatment fluid F-23 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 3 7 35 Treatment fluid F-24 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 1 9 40 Treatment fluid F-25 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 9 1 8 Treatment fluid F-26 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 twenty three Treatment fluid F-27 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 5 5 28 Treatment fluid F-28 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 3 7 33 Treatment fluid F-29 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 1 9 38

[Table 29] Table 11 Treatment fluid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) Type CAS SP value ΔD ΔP ΔH Type CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid F-30 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 9 1 9 Treatment fluid F-31 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 7 3 twenty three Treatment fluid F-32 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 5 5 28 Treatment fluid F-33 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 3 7 34 Treatment fluid F-34 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 1-Heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 1 9 39 Treatment fluid F-35 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 9 1 11 Treatment fluid F-36 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 7 3 27 Treatment fluid F-37 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 5 5 32 Treatment fluid F-38 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 3 7 38 Treatment fluid F-39 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 7-Octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 1 9 44 Treatment fluid F-40 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 9 1 15 Treatment fluid F-41 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 5 5 45 Treatment fluid F-42 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 3 7 75 Treatment fluid F-43 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 1 9 110 Treatment fluid F-44 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 9 1 15 Treatment fluid F-45 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 5 5 45 Treatment fluid F-46 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 3 7 75 Treatment fluid F-47 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 1 9 110 Treatment fluid F-48 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 9 1 10 Treatment fluid F-49 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 5 5 40 Treatment fluid F-50 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 3 7 60 Treatment fluid F-51 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 1 9 80 Treatment fluid F-52 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 9 1 10 Treatment fluid F-53 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 5 5 40 Treatment fluid F-54 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 3 7 60 Treatment fluid F-55 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 1 9 80 Treatment fluid F-56 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 30 Treatment fluid F-57 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 30 Treatment fluid F-58 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 7 3 15

[Table 30] Table 11 Treatment fluid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) Type CAS SP value ΔD ΔP ΔH Type CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid F-59 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 20 Treatment fluid F-60 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 9 1 10 Treatment fluid F-61 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 25 Treatment fluid F-62 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 5 5 30 Treatment fluid F-63 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 3 7 35 Treatment fluid F-64 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3-Octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 1 9 40 Treatment fluid F-65 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 9 1 10 Treatment fluid F-66 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid F-67 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 5 5 30 Treatment fluid F-68 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 3 7 35 Treatment fluid F-69 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 1-Octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 1 9 40 Treatment fluid F-70 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 9 1 8 Treatment fluid F-71 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 twenty three Treatment fluid F-72 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 5 5 28 Treatment fluid F-73 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 3 7 33 Treatment fluid F-74 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 1 9 38 Treatment fluid F-75 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 15 Treatment fluid F-76 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 20 Treatment fluid F-77 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 9 1 15 Treatment fluid F-78 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 5 5 45 Treatment fluid F-79 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 3 7 75 Treatment fluid F-80 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 1 9 110 Treatment fluid F-81 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 9 1 15 Treatment fluid F-82 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 5 5 45 Treatment fluid F-83 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 3 7 75 Treatment fluid F-84 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 1 9 110

[Table 31] Table 11 Treatment fluid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) Type CAS SP value ΔD ΔP ΔH Type CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid F-85 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 9 1 10 Treatment fluid F-86 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 5 5 40 Treatment fluid F-87 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 3 7 60 Treatment fluid F-88 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 1 9 80 Treatment fluid F-89 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 9 1 10 Treatment fluid F-90 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 5 5 40 Treatment fluid F-91 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 3 7 60 Treatment fluid F-92 3-Octanone 106-68-3 17.5 65.3 18.1 16.5 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 1 9 80 Treatment fluid RF-1 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 2-Butanol 78-92-2 20.7 43.9 15.8 40.3 0.6 9 1 15 Treatment fluid RF-2 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 4-Methyl-2-pentanol 108-11-2 21.1 51.5 14.5 34.0 1.5 9 1 20 Treatment fluid RF-3 Diisobutyl Ketone 108-83-8 17.4 69.7 18.6 11.8 Benzyl alcohol 100-51-6 21.1 47.9 16.4 35.7 1.1 9 1 25 Treatment fluid RF-4 2-Heptanone 110-43-0 18.1 61.9 21.9 16.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 30 Treatment fluid RF-5 2-Heptanone 110-43-0 18.1 61.9 21.9 16.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 30 Treatment fluid RF-6 2-Heptanone 110-43-0 18.1 61.9 21.9 16.2 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 7 3 15 Treatment fluid RF-7 2-Heptanone 110-43-0 18.1 61.9 21.9 16.2 2-Octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 20 Treatment fluid RF-8 2-Heptanone 110-43-0 18.1 61.9 21.9 16.2 3-Ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 15 Treatment fluid RF-9 2-Heptanone 110-43-0 18.1 61.9 21.9 16.2 2-Ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 20

[Table 32] Table 12 Type of treatment fluid Evaluation results Resolution Exposure film damage Bridging Defect Resistivity Dense pattern DOT logo Sparse pattern Example F-1 Treatment fluid F-1 B B B A A A Example F-2 Treatment fluid F-2 B B B A A A Example F-3 Treatment fluid F-3 B B B A A A Example F-4 Treatment fluid F-4 B B B A B A Example F-5 Treatment fluid F-5 A A A A A C Example F-6 Treatment fluid F-6 A B A A B A Example F-7 Treatment fluid F-7 A A A A A C Example F-8 Treatment fluid F-8 A A A A A C Example F-9 Treatment fluid F-9 A A A A A C Example F-10 Treatment fluid F-10 A A A A A C Example F-11 Treatment fluid F-11 A B A A A A Example F-12 Treatment fluid F-12 A B A A A A Example F-13 Treatment fluid F-13 A B A A A A Example F-14 Treatment fluid F-14 B C B A A A Example F-15 Treatment fluid F-15 A A A A A A Example F-16 Treatment fluid F-16 A A A A A A Example F-17 Treatment fluid F-17 A A A A A A Example F-18 Treatment fluid F-18 A B A A A A Example F-19 Treatment fluid F-19 B B A A A A Example F-20 Treatment fluid F-20 A A A A A A Example F-21 Treatment fluid F-21 A A A A A A Example F-22 Treatment fluid F-22 A A A A A A Example F-23 Treatment fluid F-23 A A A A A A Example F-24 Treatment fluid F-24 A A A A A A Example F-25 Treatment fluid F-25 A A A A A A Example F-26 Treatment fluid F-26 A A A A A A Example F-27 Treatment fluid F-27 A B A A A A Example F-28 Treatment fluid F-28 A B A A A A Example F-29 Treatment fluid F-29 B B A A A A Example F-30 Treatment fluid F-30 A A A A A A Example F-31 Treatment fluid F-31 A A A A A A Example F-32 Treatment fluid F-32 A A A A A A Example F-33 Treatment fluid F-33 A A A A A A Example F-34 Treatment fluid F-34 A A A A A A Example F-35 Treatment fluid F-35 A A A A A A Example F-36 Treatment fluid F-36 A A A A A A Example F-37 Treatment fluid F-37 A A A A A A Example F-38 Treatment fluid F-38 A B A A A A Example F-39 Treatment fluid F-39 B B A A A A Example F-40 Treatment fluid F-40 B B B A A A

[Table 33] Table 12 Type of treatment fluid Evaluation results Resolution Exposure film damage Bridging Defect Resistivity Dense pattern DOT logo Sparse pattern Example F-41 Treatment fluid F-41 B B B A A A Example F-42 Treatment fluid F-42 C C B A A A Example F-43 Treatment fluid F-43 C C B A A A Example F-44 Treatment fluid F-44 B B B A A A Example F-45 Treatment fluid F-45 B C B A A A Example F-46 Treatment fluid F-46 B C B A A A Example F-47 Treatment fluid F-47 B C C A A A Example F-48 Treatment fluid F-48 B B B A A A Example F-49 Treatment fluid F-49 B B B A A A Example F-50 Treatment fluid F-50 B C B A A A Example F-51 Treatment fluid F-51 B C C A A A Example F-52 Treatment fluid F-52 B B B A B A Example F-53 Treatment fluid F-53 B B B A B A Example F-54 Treatment fluid F-54 B C B A A A Example F-55 Treatment fluid F-55 B C B A A A Example F-56 Treatment fluid F-56 B B B A A A Example F-57 Treatment fluid F-57 B B B A A A Example F-58 Treatment fluid F-58 A A A B A A Example F-59 Treatment fluid F-59 A B A A B A Example F-60 Treatment fluid F-60 A B A A A A Example F-61 Treatment fluid F-61 A B A A A A Example F-62 Treatment fluid F-62 A A A A A A Example F-63 Treatment fluid F-63 A A A A A A Embodiment F-64 Treatment fluid F-64 B A A A A A Example F-65 Treatment fluid F-65 A B A A A A Example F-66 Treatment fluid F-66 A B A A A A Example F-67 Treatment fluid F-67 A A A A A A Example F-68 Treatment fluid F-68 A A A A A A Example F-69 Treatment fluid F-69 A A A A A A Example F-70 Treatment fluid F-70 A A A A A A Example F-71 Treatment fluid F-71 A A A A A A Example F-72 Treatment fluid F-72 A A A A A A Example F-73 Treatment fluid F-73 A A A A A A Example F-74 Treatment fluid F-74 B A A A A A Example F-75 Treatment fluid F-75 B B B A A A Example F-76 Treatment fluid F-76 B B B A B A Example F-77 Treatment fluid F-77 B B B A A A Example F-78 Treatment fluid F-78 B B B A A A Example F-79 Treatment fluid F-79 C C B A A A Example F-80 Treatment fluid F-80 C C B A A A

[Table 34] Table 12 Type of treatment fluid Evaluation results Resolution Exposure film damage Bridging Defect Resistivity Dense pattern DOT logo Sparse pattern Example F-81 Treatment fluid F-81 B B B A A A Example F-82 Treatment fluid F-82 B B B A A A Example F-83 Treatment fluid F-83 B B B A A A Example F-84 Treatment fluid F-84 B C C A A A Example F-85 Treatment fluid F-85 B B B A A A Example F-86 Treatment fluid F-86 B C B A A A Example F-87 Treatment fluid F-87 B C B A A A Example F-88 Treatment fluid F-88 B C C A A A Example F-89 Treatment fluid F-89 B B B A B A Example F-90 Treatment fluid F-90 B B B A B A Example F-91 Treatment fluid F-91 B C B A A A Example F-92 Treatment fluid F-92 B C B A A A Comparative Example F-1 Treatment fluid RF-1 E E E E A A Comparative Example F-2 Treatment fluid RF-2 D E D E A A Comparative Example F-3 Treatment fluid RF-3 D E D E A A Comparative Example F-4 Treatment fluid RF-4 E E D B A B Comparative Example F-5 Treatment fluid RF-5 E E D B A B Comparative Example F-6 Treatment fluid RF-6 D D D B A A Comparative Example F-7 Treatment fluid RF-7 D E D B B A Comparative Example F-8 Treatment fluid RF-8 D E D B A A Comparison Example F-9 Treatment fluid RF-9 D E D B B A

The results in Table 12 confirm that the processing solution of the embodiment (the processing solution containing a ketone solvent as solvent A-2 and an alcohol solvent as solvent B-1) can form a pattern in which pattern collapse is suppressed, film loss in the exposure part is suppressed, and bridge defects are suppressed. In addition, it is confirmed that the processing solution of the embodiment has a low resistivity and excellent safety. Furthermore, the results in Table 12 demonstrate that when the second organic solvent comprises one or more selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2-octanol and 2,6-dimethyl-4-heptanol, one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or an acyclic alcohol solvent having a triple bond in the molecule (preferably one or more selected from 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol), the suppression of pattern collapse and the suppression of bridging defects are more excellent. Among them, the results in Table 12 prove that when 2-octanol, any one or more of 2,6-dimethyl-4-heptanol and 3-octanol are included, or when a non-cyclic alcohol solvent having a triple bond in the molecule is included (preferably one or more selected from 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol), regardless of the type of the first organic solvent and the mixing ratio of the first organic solvent to the second organic solvent, the suppression of pattern collapse and the suppression of bridging defects are still excellent. Furthermore, the results in Table 12 confirm that when the second organic solvent contains 3,7-dimethyl-3-octanol and the content of the first organic solvent is 40 to 80 mass % relative to the total content of the first organic solvent and the second organic solvent, a pattern collapse can be further suppressed, film loss in the exposure part can be further suppressed, and a pattern with bridge defects can be further suppressed. Furthermore, the results in Table 12 demonstrate that when the second organic solvent includes one or more selected from 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, and 2-octanol, and the content of the first organic solvent is 20 to 80 mass % relative to the total content of the first organic solvent and the second organic solvent, a pattern in which pattern collapse is further suppressed, film loss in the exposed portion is further suppressed, and bridging defects are further suppressed can be formed.

Furthermore, the results in Table 12 confirm that when the second organic solvent is 2-ethyl-1-hexanol and the content of the first organic solvent is less than 40 mass % relative to the total content of the first organic solvent and the second organic solvent, a pattern in which pattern collapse is further suppressed, film loss in the exposed portion is further suppressed, and bridging defects are further suppressed can be formed.

Furthermore, the results of Tables 2, 4, 6, 8, 10 and 12 confirmed that when solvent A was solvent A-1 selected from hydrocarbon solvents and ether solvents, and solvent B was solvent B-1 (alcohol solvent), a pattern in which pattern collapse was further suppressed could be formed.

[Pattern formation (EUV exposure, negative development) and evaluation 2] In the pattern formation of Example A-1, the pattern formation was carried out in the same manner except that butyl acetate as the developer was changed to the processing solution A-1 shown in Table 1.

[Pattern formation (EUV exposure, negative development) and evaluation 3] In the pattern formation of Example A-2, the pattern formation was carried out in the same manner except that butyl acetate as the developer was changed to the processing solution A-2 shown in Table 1.

[Pattern formation (EUV exposure, negative development) and evaluation 4] In the pattern formation of Example A-3, the pattern formation was carried out in the same manner except that butyl acetate as the developer was changed to the processing solution A-3 shown in Table 1.

[Pattern formation (EUV exposure, negative development) and evaluation 5] In the pattern formation of Example E-1, the pattern formation was carried out in the same manner except that isobutyl isobutyrate in the processing liquid E-1 was changed to isobutyl butyrate.

[Pattern formation (EUV exposure, negative development) and evaluation 6] In the treatment liquid E-1 (Example E-1) shown in Table 9, except that isobutyl isobutyrate as the first organic solvent was replaced with isobutyl butyrate or butyl isobutyrate, treatment liquid E-1-1 and treatment liquid E-1-2 were prepared in the same manner and the same evaluation as treatment liquid E-1 was carried out. As a result, the same results as treatment liquid E-1 (Example E-1) were obtained.

[Pattern formation (EUV exposure, negative development) and evaluation 7] (Example A-1') Resist composition 2 was prepared by the same method as resist composition 1 except that the following resin (A-2) was used instead of resin (A-1).

[Chemical formula 70]

The composition ratio (molar ratio) of each repeating unit in the above resin (A-2) is 60/40 from left to right. The above molar ratio is calculated by ¹ H-NMR measurement. In addition, the weight average molecular weight (Mw) of the standard polystyrene converted by gel permeation chromatography (GPC) (solvent: THF) of the resin (A-2) is 11,000, and the molecular weight dispersion (Mw/Mn) is 1.60.

Except that the resist composition 2 was used instead of the resist composition 1, the pattern was formed and evaluated in the same order as in Example A-1. As a result, the evaluation of pattern collapse was as follows: C for dense pattern, C for DOT pattern, C for sparse pattern, A for film damage in the exposed part, and A for bridging defects. Comparison between Example A-1 and Example A-1' confirmed that the effect of the present invention can be further exerted when the resin contains the repeating unit (hydroxystyrene-based repeating unit) represented by the above general formula (1).

without.

without

without.

Claims (12)

A treatment liquid for developing and cleaning a resist film obtained by photosensitive radiation or a radiation-sensitive composition, and containing an organic solvent for resist film patterning, the treatment liquid containing: a first organic solvent satisfying the following condition A and a second organic solvent satisfying the following condition B, condition A: an ether solvent having an SP value of 18.7 MPa ^1/2 or less and a ΔP represented by the following formula (1) of 15.0 or less, condition B: an SP value of 19.0 MPa ^1/2 or more and an alcoholic solvent with a ClogP of 1.6 or more, formula (1): ΔP=δp/(δd+δp+δh)×100, wherein δd represents the dispersion term of the Hansen solubility parameter, δp represents the polar term of the Hansen solubility parameter, and δh represents the hydrogen bond term of the Hansen solubility parameter, wherein the first organic solvent comprises at least one selected from diamyl ether, diisoamyl ether, dibutyl ether, diisobutyl ether and diisopropyl ether, and the first The second organic solvent comprises at least one selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2,6-dimethyl-4-heptanol, 2-ethyl-1-hexanol, 1-heptanol, 2-octanol, 1-octanol, 1-hexanol, 3-octanol, 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol. The treatment liquid as described in claim 1, wherein the second organic solvent comprises one or more non-cyclic alcohol solvents selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2,6-dimethyl-4-heptanol, 2-ethyl-1-hexanol, 1-heptanol, 2-octanol, 1-octanol and 1-hexanol. The treatment liquid as described in claim 1, wherein the second organic solvent comprises one or more non-cyclic alcohol solvents selected from 2,6-dimethyl-4-heptanol and 3-octanol. The treatment liquid as described in claim 1, wherein the second organic solvent comprises one or more non-cyclic alcohol solvents having a triple bond in the molecule selected from 1-octyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-heptyne-3-ol and 7-octyne-1-ol. The treatment liquid as described in any one of claim 1 to claim 4, wherein the first organic solvent contains at least one of diisoamyl ether and diisobutyl ether. The treatment liquid as described in any one of claim 1 to claim 4, wherein the treatment liquid is a flushing liquid. The treatment solution as described in any one of claims 1 to 4, wherein the aforementioned actinic radiation or radiation-sensitive composition comprises a resin having a repeating unit represented by the following general formula (1):

In the formula, A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group, R represents a substituent, a represents an integer from 1 to 3, and b represents an integer from 0 to (5-a). In addition, when there are multiple Rs, they may be the same or different from each other, and the multiple Rs may be bonded to each other to form a ring. A pattern forming method, comprising: a resist film forming step, using photosensitive radiation or a radiation-sensitive composition to form a resist film; an exposure step, exposing the resist film; and a treatment step, treating the resist film after exposure by using a treatment solution described in any one of claim 1 to claim 6. A pattern forming method, comprising: a resist film forming step, using photosensitive radiation or a radiation-sensitive composition to form a resist film; an exposure step, exposing the resist film; and a treatment step, treating the resist film after exposure, wherein the treatment step comprises: a developing step, developing with a developer; and a rinsing step, washing with a rinse solution, wherein the rinse solution is a treatment solution described in any one of claim 1 to claim 6. A pattern forming method as described in claim 9, wherein the aforementioned developer contains an ester solvent. The pattern forming method as described in claim 10, wherein the aforementioned ester solvent comprises one or more selected from butyl acetate, pentyl acetate, isopentyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, butyl butyrate, butyl isobutyrate and isobutyl isobutyrate. The pattern forming method as described in any one of claim 8 to claim 11, wherein the aforementioned actinic radiation or radiation-sensitive composition comprises a resin having a repeating unit represented by the following general formula (1):

In the formula, A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group, R represents a substituent, a represents an integer from 1 to 3, and b represents an integer from 0 to (5-a). In addition, when there are multiple Rs, they may be the same or different from each other, and the multiple Rs may be bonded to each other to form a ring.