Chemical solution, resist pattern forming method, semiconductor chip manufacturing method, chemical solution container, and chemical solution manufacturing method

Abstract

To provide a chemical liquid that demonstrates excellent defect inhibition performance when it is used as a prewet solution, and provide a resist pattern formation method, a semiconductor chip manufacturing method, a chemical liquid storage body, and a chemical liquid manufacturing method.SOLUTION: A chemical liquid according to the present invention is used as a prewet solution and contains cyclohexanone and at least one first compound selected from the group consisting of a compound represented by General Formula (1), a compound represented by General Formula (2), and a compound represented by General Formula (3), in which the content of the cyclohexanone is 98.000 to 99.999 mass% with respect to the total mass of the chemical liquid, and the total content of the first compounds is 0.001 to 100 mass ppm with respect to the total mass of the chemical liquid.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a chemical solution, a resist pattern forming method, a semiconductor chip manufacturing method, a chemical solution container, and a chemical solution manufacturing method. [Background technology]

[0002] When manufacturing semiconductor devices, a chemical liquid containing an organic solvent is used as a pre-wet liquid. In recent years, with the increasing sophistication of semiconductor products, the above-mentioned chemicals used in semiconductor manufacturing are required to have even greater defect suppression properties.

[0003] As a chemical liquid used as a pre-wet liquid, Patent Document 1 lists "a pre-wet agent (claim 1) that is a solvent that dissolves the coating liquid supplied to the substrate to be treated and has a viscosity of 2.0 cP (centipoise) or more," and lists cyclohexanone as a specific example (claim 5). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-039828 Summary of the Invention [Problem to be solved by the invention]

[0005] The present inventors have found that there is room for improvement in suppressing the occurrence of defects when the prewetting agent is applied to the manufacturing process of semiconductor devices. Therefore, an object of the present invention is to provide a chemical liquid that has excellent defect suppression properties when used as a pre-wet liquid. Another object of the present invention is to provide a resist pattern forming method, a semiconductor chip manufacturing method, a chemical solution container, and a chemical solution manufacturing method. [Means for solving the problem]

[0006] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by the following configuration.

[0007] [1] Cyclohexanone and A drug solution containing one or more first compounds selected from the group consisting of a compound represented by general formula (1), a compound represented by general formula (2), and a compound represented by general formula (3), the content of the cyclohexanone is 98.000 to 99.999% by mass relative to the total mass of the chemical solution, the total content of the first compound is 0.001 to 100 ppm by mass relative to the total mass of the chemical solution; A chemical liquid used as a pre-wet liquid.

[0008] [ka]

[0009] [2] The chemical solution according to [1], wherein the content of the compound represented by the general formula (1) in the chemical solution is 0.01 to 70 ppm by mass relative to the total mass of the chemical solution. [3] The chemical solution according to [1] or [2], wherein the total content of the first compound in the chemical solution is 0.005 to 95 ppm by mass with respect to the total mass of the chemical solution. [4] The chemical solution according to any one of [1] to [3], wherein the mass ratio of the content of the compound represented by the general formula (1) to the content of the compound represented by the general formula (2) in the chemical solution is 1 to 500. [5] The chemical solution according to any one of [1] to [4], wherein the mass ratio of the content of the compound represented by the general formula (1) to the content of the compound represented by the general formula (3) in the chemical solution is 1 to 3,000. [6] The chemical solution according to any one of [1] to [5], wherein the mass ratio of the content of the compound represented by the general formula (2) to the content of the compound represented by the general formula (3) in the chemical solution is 1 to 150. [7] Further, the composition contains one or more hydroxycyclohexanones selected from the group consisting of 2-hydroxycyclohexanone, 3-hydroxycyclohexanone, and 4-hydroxycyclohexanone, The chemical solution according to any one of [1] to [6], wherein the total content of the hydroxycyclohexanone is 0.001 to 1000 ppm by mass relative to the total mass of the chemical solution. [8] The chemical solution according to [7], wherein the mass ratio of the content of the 2-hydroxycyclohexanone to the content of the 3-hydroxycyclohexanone in the chemical solution is 0.005 to 300. [9] The chemical solution according to [7] or [8], wherein the mass ratio of the content of the 2-hydroxycyclohexanone to the content of the 4-hydroxycyclohexanone in the chemical solution is 0.01 to 15.

[10] The chemical solution according to any one of [7] to [9], wherein the mass ratio of the content of the 3-hydroxycyclohexanone to the content of the 4-hydroxycyclohexanone in the chemical solution is 0.003 to 100.

[11] Further, it contains 1,2-cyclohexanedione, The chemical solution according to any one of [1] to

[10] , wherein the content of the 1,2-cyclohexanedione is 0.0005 to 40 ppm by mass relative to the total mass of the chemical solution.

[12] Further, it contains cyclohexanol, The chemical solution according to any one of [1] to

[11] , wherein the content of the cyclohexanol is 0.0003 to 30 ppm by mass relative to the total mass of the chemical solution.

[13] Furthermore, it contains 1-hexanoic acid, The chemical solution according to any one of [1] to

[12] , wherein the content of the 1-hexanoic acid is 5 to 600 ppm by mass relative to the total mass of the chemical solution.

[14] Contains 1,2-cyclohexanedione and cyclohexanol, The chemical solution according to any one of [1] to

[13] , wherein the mass ratio of the content of the 1,2-cyclohexanedione to the content of the cyclohexanol in the chemical solution is 0.2 to 400.

[15] Contains 1,2-cyclohexanedione and 1-hexanoic acid, The chemical solution according to any one of [1] to

[14] , wherein the mass ratio of the content of the 1,2-cyclohexanedione to the content of the 1-hexanoic acid in the chemical solution is 0.005 to 5.

[16] Contains cyclohexanol and 1-hexanoic acid, The chemical solution according to any one of [1] to

[15] , wherein the mass ratio of the content of the cyclohexanol to the content of the 1-hexanoic acid in the chemical solution is 0.0005 to 0.5.

[17] Further, the composition contains one or more second compounds selected from the group consisting of compounds represented by general formula (4) and compounds represented by general formula (5), The chemical solution according to any one of [1] to

[16] , wherein the total content of the second compounds is 0.5 to 10 ppm by mass with respect to the total mass of the chemical solution.

[0010] [ka]

[0011]

[18] Furthermore, it contains a high-boiling organic compound having a boiling point of 450°C or higher, The chemical solution according to any one of [1] to

[17] , wherein the content of the high-boiling organic compound is 10 to 1000 ppb by mass relative to the total mass of the chemical solution.

[19] Further, the composition contains one or more metal components selected from the group consisting of particulate metal components and ionic metal components, The chemical solution according to any one of [1] to

[18] , wherein the total content of the metal components is 10 to 350 mass ppt relative to the total mass of the chemical solution.

[20] The present invention comprises a particulate metal component containing Fe and having a particle size of 15 to 20 nm, and a particulate metal component containing Pd and having a particle size of 15 to 20 nm, The chemical solution according to

[19] , wherein the mass ratio of the content of the particulate metal component containing Fe and having a particle size of 15 to 20 nm to the content of the particulate metal component containing Pd and having a particle size of 15 to 20 nm in the chemical solution is 1 to 23. 〔twenty one〕 A substrate on which an actinic ray-sensitive or radiation-sensitive resin composition is applied to form a resist film, The chemical solution according to any one of [1] to

[20] , which is a pre-wetting solution that is applied onto the substrate before the actinic ray-sensitive or radiation-sensitive resin composition is applied. 〔twenty two〕 A step of applying the chemical solution according to

[21] onto the substrate; a step of applying the actinic ray-sensitive or radiation-sensitive resin composition onto the substrate that has been subjected to the prewetting step to form a resist film; exposing the resist film to light; and developing the exposed resist film with a developer to obtain a resist pattern. 〔twenty three〕 A method for manufacturing a semiconductor chip, comprising the method for forming a resist pattern according to

[22] . 〔twenty four〕 A drug solution container containing a container and the drug solution according to any one of [1] to

[21] contained in the container, A chemical solution container, wherein a liquid-contacting portion that comes into contact with the chemical solution in the container is formed of electropolished stainless steel or fluorine-based resin. 〔twenty five〕 The drug solution container according to

[24] , wherein the void ratio within the container calculated by formula (1) is 1 to 20% by volume. Equation (1): Porosity = {1 - (volume of the chemical solution in the container / volume of the container)} x 100

[26] A method for producing a chemical solution according to any one of [1] to

[21] , wherein a material to be purified containing cyclohexanone is purified to obtain the chemical solution according to any one of [1] to

[21] , A method for producing a chemical solution, comprising a distillation step of distilling the product to be purified. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a chemical liquid that has excellent defect suppression properties when used as a pre-wet liquid. It is also possible to provide a resist pattern forming method, a semiconductor chip manufacturing method, a chemical solution container, and a chemical solution manufacturing method. DETAILED DESCRIPTION OF THE INVENTION

[0013] The present invention will be described in detail below. The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the present invention, "ppm" stands for "parts-per-million (10 -6 ) and "ppb" stands for "parts-per-billion (10 -9 ) and "ppt" stands for "parts-per-trillion (10 -12 )" Furthermore, in the description of groups (atomic groups) in the present invention, when a notation does not specify whether they are substituted or unsubstituted, it encompasses both groups that do not have a substituent and groups that contain a substituent, as long as it does not impair the effects of the present invention. For example, the term "hydrocarbon group" encompasses not only hydrocarbon groups that do not have a substituent (unsubstituted hydrocarbon groups), but also hydrocarbon groups that contain a substituent (substituted hydrocarbon groups). This also applies to each compound. In the present invention, "radiation" refers to, for example, far ultraviolet, extreme ultraviolet (EUV), X-rays, or electron beams. In the present invention, "light" refers to actinic rays or radiation. Unless otherwise specified, "exposure" in the present invention includes not only exposure with far ultraviolet, X-rays, EUV, or the like, but also writing with particle beams such as electron beams or ion beams.

[0014] [Chemical solution] The drug solution of the present invention comprises: Cyclohexanone and A drug solution containing one or more first compounds selected from the group consisting of a compound represented by general formula (1) described below, a compound represented by general formula (2) described below, and a compound represented by general formula (3) described below, The content of cyclohexanone is 98.000 to 99.999% by mass relative to the total mass of the chemical solution, the total content of the first compound is 0.001 to 100 ppm by mass relative to the total mass of the chemical solution; This is a chemical liquid used as a pre-wet liquid. The mechanism by which the problem of the present invention is solved by the chemical solution of the present invention having such a configuration is not entirely clear, but the present inventors speculate on this mechanism as follows. That is, when a chemical solution containing cyclohexanone contains a predetermined amount or more of a compound (first compound) represented by the general formulas (1) to (3) described below, the first compound interacts with residues that cause defects, and residues that cause defects are unlikely to remain on a workpiece (substrate, etc.) treated with the chemical solution. On the other hand, when the content of the first compound in the chemical solution is a predetermined amount or less, the first compound and cyclohexanone are sufficiently compatible with each other, and it is therefore believed that the first compound itself can be prevented from forming residues that cause defects. Furthermore, the chemical solution of the present invention is excellent in stability over time and in terms of resist composition saving performance.

[0015] The components contained in the medicinal solution of the present invention will be described in detail below.

[0016] <Cyclohexanone> The chemical solution contains cyclohexanone, which is a compound represented by the following structural formula:

[0017] [ka]

[0018] The content of cyclohexanone in the chemical solution is 98.000 to 99.999 mass% relative to the total mass of the chemical solution, and from the standpoint of achieving better defect suppression, stability over time, and / or resist composition-saving performance (hereinafter simply referred to as "better effects of the present invention"), a content of 99.000 to 99.990 mass% is more preferable, and a content of 99.300 to 99.900 mass% is even more preferable. The contents of cyclohexanone and organic components such as the compounds of Formulas 1 to 5, hydroxycyclohexanone, 1,2-cyclohexanedione, cyclohexanol, 1-hexanoic acid, and high-boiling organic compounds in the chemical solution are determined by gas chromatography mass spectrometry (GC / MS). Specifically, these can be measured using an Agilent GC: 7890B, MS: 5977B EI / CI MSD, etc.

[0019] <First compound> The drug solution contains one or more first compounds selected from the group consisting of a compound represented by general formula (1) (hereinafter also referred to as "formula 1 compound"), a compound represented by general formula (2) (hereinafter also referred to as "formula 2 compound"), and a compound represented by general formula (3) (hereinafter also referred to as "formula 3 compound").

[0020] [ka]

[0021] The total content of the first compound in the chemical solution (that is, the total content of the compound of formula 1, the compound of formula 2, and the compound of formula 3) is 0.001 to 100 ppm by mass relative to the total mass of the chemical solution. Among these, the content is preferably 0.005 to 95 ppm by mass, and more preferably 0.005 to 70 ppm by mass, in terms of achieving better effects of the present invention.

[0022] The content of the compound of formula 1 is preferably 0.01 to 95 ppm by mass, more preferably 0.01 to 70 ppm by mass, relative to the total mass of the chemical solution. The content of the compound of formula 2 is preferably 0.001 to 20 ppm by mass, more preferably 0.001 to 10 ppm by mass, relative to the total mass of the chemical solution. The content of the compound of formula 3 is preferably 0.0005 to 10 ppm by mass, more preferably 0.0005 to 5 ppm by mass, relative to the total mass of the chemical solution.

[0023] In the chemical solution, the mass ratio of the content of the compound of formula 1 to the content of the compound of formula 2 (content of the compound of formula 1 / content of the compound of formula 2) is preferably 0.5-1,000, more preferably 1-500. In the chemical solution, the mass ratio of the content of the compound of formula 1 to the content of the compound of formula 3 (content of the compound of formula 1 / content of the compound of formula 3) is preferably 0.5 to 5,000, more preferably 1 to 3,000. In the chemical solution, the mass ratio of the content of the compound of formula 2 to the content of the compound of formula 3 (content of the compound of formula 2 / content of the compound of formula 3) is preferably 0.01-300, more preferably 1-150. When these ratios are within the above ranges, the effects of the present invention are more excellent.

[0024] <Hydroxycyclohexanone> In terms of achieving better effects of the present invention, it is preferable that the chemical solution further contains one or more hydroxycyclohexanones selected from the group consisting of 2-hydroxycyclohexanone, 3-hydroxycyclohexanone, and 4-hydroxycyclohexanone. 2-Hydroxycyclohexanone, 3-hydroxycyclohexanone, and 4-hydroxycyclohexanone are compounds represented by the following structural formulas (in order from left to right):

[0025] [ka]

[0026] In order to achieve better effects of the present invention, the total content of hydroxycyclohexanones in the chemical solution (i.e., the total content of 2-hydroxycyclohexanone, 3-hydroxycyclohexanone, and 4-hydroxycyclohexanone) is preferably 0.001 to 2500 mass ppm, and more preferably 0.001 to 1000 mass ppm, relative to the total mass of the chemical solution. The inventors believe that when the chemical solution contains a predetermined amount or more of hydroxycyclohexanone, the hydroxycyclohexanone interacts with residues that cause defects, making it difficult for residues that cause defects to remain on the object (substrate, etc.) treated with the chemical solution. On the other hand, when the content of hydroxycyclohexanone in the chemical solution is a predetermined amount or less, the hydroxycyclohexanone and cyclohexanone are sufficiently compatible with each other, making it possible to prevent the hydroxycyclohexanone itself from forming residues that cause defects.

[0027] In addition, in terms of achieving better effects of the present invention, the content of 2-hydroxycyclohexanone is preferably 0.005 to 1500 ppm by mass, more preferably 0.5 to 20 ppm by mass, relative to the total mass of the chemical solution. The content of 3-hydroxycyclohexanone is preferably 0.1 to 70 ppm by mass, more preferably 0.2 to 5 ppm by mass, relative to the total mass of the chemical solution. The content of 4-hydroxycyclohexanone is preferably 0.001 to 2500 ppm by mass, more preferably 10 to 300 ppm by mass, relative to the total mass of the chemical solution.

[0028] In the chemical solution, the mass ratio of the content of 2-hydroxycyclohexanone to the content of 3-hydroxycyclohexanone (content of 2-hydroxycyclohexanone / content of 3-hydroxycyclohexanone) is preferably 0.005 to 2000, more preferably 0.005 to 300. In the chemical solution, the mass ratio of the content of 2-hydroxycyclohexanone to the content of 4-hydroxycyclohexanone (content of 2-hydroxycyclohexanone / content of 4-hydroxycyclohexanone) is preferably 0.00001-100, more preferably 0.01-15. In the chemical solution, the mass ratio of the content of 3-hydroxycyclohexanone to the content of 4-hydroxycyclohexanone (content of 3-hydroxycyclohexanone / content of 4-hydroxycyclohexanone) is preferably 0.00005-300, more preferably 0.003-100. When these ratios are within the above ranges, the effects of the present invention are more excellent.

[0029] <1,2-cyclohexanedione, cyclohexanol, 1-hexanoic acid> In terms of achieving better effects of the present invention, it is preferable that the chemical solution further contains one or more compounds selected from the group consisting of 1,2-cyclohexanedione, cyclohexanol, and 1-hexanoic acid. 1,2-Cyclohexanedione, cyclohexanol, and 1-hexanoic acid are compounds represented by the following structural formulas (from left to right):

[0030] [ka]

[0031] In order to obtain a more excellent effect of the present invention, the content of 1,2-cyclohexanedione is preferably 0.0005 to 1500 ppm by mass, and more preferably 0.0005 to 40 ppm by mass, relative to the total mass of the chemical solution. The content of cyclohexanol is preferably 0.0003 to 75 ppm by mass, more preferably 0.0003 to 30 ppm by mass, relative to the total mass of the chemical solution. The content of 1-hexanoic acid is preferably 0.0005 to 2500 ppm by mass, more preferably 5 to 600 ppm by mass, relative to the total mass of the chemical solution. The inventors believe that when the chemical solution contains a predetermined amount or more of the above-mentioned compound (1,2-cyclohexanedione, cyclohexanol, or 1-hexanoic acid), the compound interacts with residues that cause defects, making it difficult for residues that cause defects to remain on the object (substrate, etc.) treated with the chemical solution. On the other hand, when the content of the above-mentioned compound in the chemical solution is a predetermined amount or less, the chemical solution is sufficiently compatible with the above-mentioned compound, and therefore it is believed that the compound itself can be prevented from forming residues that cause defects.

[0032] In the chemical solution, the mass ratio of the content of 1,2-cyclohexanedione to the content of cyclohexanol (1,2-cyclohexanedione content / cyclohexanol content) is preferably 0.01 to 3,000, more preferably 0.2 to 400. In the chemical solution, the mass ratio of the content of 1,2-cyclohexanedione to the content of 1-hexanoic acid (1,2-cyclohexanedione content / 1-hexanoic acid content) is preferably 0.05 to 100, and more preferably 0.005 to 5. In the chemical solution, the mass ratio of the cyclohexanol content to the 1-hexanoic acid content (cyclohexanol content / 1-hexanoic acid content) is preferably 0.00005 to 50, more preferably 0.0005 to 0.5. When these ratios are within the above ranges, the effects of the present invention are more excellent.

[0033] <Second compound> In order to obtain a more excellent effect of the present invention, it is preferable that the chemical solution further contains one or more second compounds selected from the group consisting of a compound represented by general formula (4) (hereinafter also referred to as "formula 4 compound") and a compound represented by general formula (5) (hereinafter also referred to as "formula 5 compound").

[0034] [ka]

[0035] In order to obtain better effects of the present invention, the total content of the second compound in the chemical solution (total content of the compound of formula 4 and the compound of formula 5) is preferably 0.0001 to 1500 mass ppm, more preferably 0.5 to 10 mass ppm, relative to the total mass of the chemical solution. The inventors believe that when the second compound is contained in a predetermined amount or more, the second compound interacts with residues that cause defects, making it difficult for residues that cause defects to remain on the object (substrate, etc.) treated with the chemical solution. On the other hand, when the content of the second compound in the chemical solution is a predetermined amount or less, the second compound and cyclohexanone are sufficiently compatible with each other, making it possible to prevent the second compound itself from forming residues that cause defects.

[0036] In order to obtain a more excellent effect of the present invention, the content of the compound of formula 4 is preferably 0.0001 to 1500 ppm by mass, more preferably 0.0001 to 5 ppm by mass, relative to the total mass of the chemical solution. The content of the compound of formula 5 is preferably 0.0001 to 100 ppm by mass, more preferably 0.0001 to 6 ppm by mass, relative to the total mass of the chemical solution.

[0037] <High boiling point organic compounds> In order to obtain a more excellent effect of the present invention, the chemical solution preferably contains a high-boiling organic compound having a boiling point of 450° C. or higher. The high-boiling organic compound is a compound other than cyclohexanone derivatives (compounds of formulas 1 to 5, hydroxycyclohexanone, 1,2-cyclohexanedione, cyclohexanol, and 1-hexanoic acid). In this specification, the boiling point means the boiling point at standard atmospheric pressure. In order to obtain a more excellent effect of the present invention, the content (total content) of the high-boiling organic compounds in the chemical solution is preferably 0.001 to 1500 mass ppb, more preferably 10 to 1000 mass ppb, relative to the total mass of the chemical solution. It is believed that when the chemical solution contains a predetermined amount or more of the high-boiling-point organic compound, it behaves like a saturated solution, making it difficult for impurities (especially impurities that are likely to cause defects) to be mixed into the chemical solution. Also, it is believed that when the content of the high-boiling-point organic compound is a predetermined amount or less, the high-boiling-point organic compound itself is unlikely to cause defects. The chemical solution may contain one kind of high-boiling point organic compound alone or two or more kinds of high-boiling point organic compounds.

[0038] <Metal components> The chemical solution may contain one or more metal components selected from the group consisting of particulate metal components (metal particles) and ionic metal components (metal ions). In the present invention, the content of the metal component refers to the total content of the metal particles and the metal ions. The chemical solution may contain either metal particles or metal ions, or may contain both.

[0039] Examples of the metal element in the metal component include Na (sodium), K (potassium), Ca (calcium), Fe (iron), Cu (copper), Mg (magnesium), Mn (manganese), Li (lithium), Al (aluminum), Cr (chromium), Ni (nickel), Ti (titanium), Zn (zirconium), and Pd (palladium). The metal component may contain one or more metal elements. The metal particles may be a simple substance, an alloy, or other metal compounds, and the metal (including metal compounds) may exist in a form associated with an organic substance. The metal ion may exist as a simple metal ion or as a complex ion (for example, an ammine complex, a cyano complex, a halogeno complex, a hydroxy complex, or the like). The metal component may be a metal component that is inevitably contained in the drug solution during production, storage, and / or transportation, or may be intentionally added.

[0040] When the chemical solution contains a metal component, the content thereof is not particularly limited, and is preferably 0.01 to 500 mass ppt, and more preferably 10 to 350 mass ppt, relative to the total mass of the chemical solution. It is believed that if the content of metal components (especially the specified metal particles described below) is equal to or greater than a specified amount, it is easier to prevent organic compounds (especially polar organic compounds) that the chemical solution may contain from agglomerating into particles on a substrate or the like and causing defects. It is also believed that if the content of the metal component is a predetermined amount or less, it is easier to avoid an increase in the occurrence of defects resulting from the metal component.

[0041] When the chemical solution contains metal particles, the content thereof is preferably 0.01 to 300 mass ppt, more preferably 1 to 250 mass ppt, relative to the total mass of the chemical solution, in order to obtain a more excellent effect of the present invention. In particular, the chemical solution preferably contains metal particles with a particle size of 15 to 20 nm. For example, the chemical solution preferably contains, as metal particles, Fe-containing metal particles (particulate metal component containing Fe) and / or Pd-containing metal particles (particulate metal component containing Pd). In order to obtain a more excellent effect of the present invention, the chemical solution preferably contains 1 to 200 mass ppt, and more preferably 2 to 100 mass ppt, of Fe-containing metal particles having a particle size of 15 to 20 nm relative to the total mass of the chemical solution. The chemical solution preferably contains 0.01 to 10 mass ppt, and more preferably 0.05 to 1 mass ppt, of metal particles containing Pd and having a particle size of 15 to 20 nm relative to the total mass of the chemical solution. In the chemical solution, the mass ratio of the content of metal particles containing Fe and having a particle size of 15 to 20 nm to the content of metal particles containing Pd and having a particle size of 15 to 20 nm (content of metal particles containing Fe and having a particle size of 15 to 20 nm / content of metal particles containing Pd and having a particle size of 15 to 20 nm) is preferably 0.5 to 50, and more preferably 1 to 23. When particles containing multiple types of metals are present, the particles are divided proportionally based on the mass ratio of the metals contained, and it is considered that particles containing each metal are present. Specifically, for example, in the case of composite metal particles containing three metals X, Y, and Z at x mass%, y mass%, and z mass%, respectively, "metal particles containing X," "metal particles containing Y," and "metal particles containing Z" are each present in masses calculated by the following formula: Mass of metal particles containing X = Mass of composite metal particles × x ÷ (x + y + z) Mass of metal particles containing Y = Mass of composite metal particles × y ÷ (x + y + z) Mass of metal particles containing Z = Mass of composite metal particles × z ÷ (x + y + z)

[0042] When the chemical solution contains metal ions, the content thereof is preferably 0.01 to 300 mass ppt, more preferably 2 to 250 mass ppt, relative to the total mass of the chemical solution, in order to obtain a more excellent effect of the present invention.

[0043] The type, particle size, and content of metal particles in the chemical solution, as well as the type and content of metal ions, can be measured by SP-ICP-MS (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry). Here, the SP-ICP-MS method uses the same equipment as the regular ICP-MS method (inductively coupled plasma mass spectrometry), but differs only in the data analysis, which can be performed using commercially available software. In ICP-MS, the content of the target metal component is measured regardless of the form of its existence. Therefore, the total mass of the target metal particles and metal ions is quantified as the content of the metal component.

[0044] On the other hand, the SP-ICP-MS method can measure the content of metal particles, so the content of metal ions in a sample can be calculated by subtracting the content of metal particles from the content of metal components in the sample. An example of an apparatus for the SP-ICP-MS method is the Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200) manufactured by Agilent Technologies, and measurements can be performed using the method described in the Examples. Other apparatuses that can be used include the NexION350S manufactured by PerkinElmer and the Agilent 8900 manufactured by Agilent Technologies.

[0045] <Water> The chemical solution may contain water in addition to the above. When the chemical solution contains water, the content thereof is preferably 1 to 3000 ppm by mass, more preferably 10 to 500 ppm by mass, relative to the total mass of the chemical solution, in terms of achieving better effects of the present invention.

[0046] <Method of manufacturing chemical solution> The method for producing the above-mentioned chemical solution is not particularly limited, and known production methods can be used. For example, a commercially available product may be purchased and purified to produce a drug solution having a predetermined composition. Alternatively, a drug solution may be produced by adding a predetermined amount of the first compound (and other components, if desired) to cyclohexanone. Among these, a preferred method for producing a chemical solution is a method in which a cyclohexanone-containing product to be purified (such as commercially available cyclohexanone) is purified to obtain a chemical solution. The purification method preferably includes at least one of a distillation step of distilling the product to be purified and a filtration step of filtering the product to be purified, more preferably a method including at least a distillation step, and even more preferably a method including both a distillation step and a filtration step. The first compound is often produced during the distillation process of cyclohexanone. Therefore, commercially available cyclohexanone that has not undergone sufficient distillation processes often contains less than the specified amount of the first compound. Therefore, the chemical solution of the present invention may be obtained by distilling a material to be purified containing cyclohexanone under predetermined conditions and adjusting the content of the first compound in the obtained chemical solution. The procedures for the distillation step and filtration step will be described in detail below.

[0047] (Distillation process) The distillation step is a step in which a product to be purified (such as a solution containing cyclohexanone) is distilled to obtain a distilled product to be purified. In the distillation step, impurities in the product to be purified can be reduced, and at the same time, the first compound is produced. The components removed by the distillation step are not particularly limited, but include, for example, water.

[0048] The content of cyclohexanone in the product to be purified that is subjected to the distillation step is preferably 98.000 to 99.999 mass % relative to the total mass of the product to be purified. The product to be purified preferably contains a predetermined amount of water. Water is thought to act as a catalyst for producing the first compound in the product to be purified that is subjected to the distillation step. From the viewpoint of adjusting the content of the first compound in the resulting chemical solution, the water content (water content) is preferably 1 to 5000 ppm, more preferably 5 to 1000 ppm by mass, relative to the total mass of the product to be purified. The method for distilling the product to be purified is not particularly limited, and known methods can be used. A typical example is a method in which a distillation column is placed on the upstream side of a purification apparatus that is subjected to the filtration step described below, and the distilled product to be purified is introduced into a production tank. In this case, the liquid-contacting parts of the distillation column are not particularly limited, but are preferably made of a corrosion-resistant material as described below.

[0049] In the distillation step, the raw material may be passed through the same distillation column multiple times, or may be passed through different distillation columns. When the raw material is passed through different distillation columns, for example, the raw material may be passed through a distillation column to undergo a crude distillation treatment for removing low-boiling point components, and then passed through a distillation column different from the crude distillation treatment to undergo a rectification treatment for removing other components, etc. Examples of the distillation column include a tray distillation column and a reduced pressure tray column. The number of theoretical plates of the distillation column is preferably 5 to 35, for example. In order to achieve both thermal stability during distillation and precision in purification, vacuum distillation may be carried out in part or in whole.

[0050] (filtration process) The filtration step is a step of filtering the product to be purified using a filter. The method for filtering the material to be purified using a filter is not particularly limited, but it is preferable to pass the material to be purified (liquid) through a filter unit having a housing and a filter cartridge housed in the housing, with or without pressure.

[0051] The pore size of the filter is not particularly limited, and a filter having a pore size normally used for filtering a material to be purified can be used. In particular, the pore size of the filter is preferably 200 nm or less, more preferably 20 nm or less, and even more preferably 10 nm or less. Although the lower limit is not particularly limited, a pore size of 1 nm or more is generally preferred from the viewpoint of productivity. In this specification, the pore size of the filter means the pore size determined by the bubble point of isopropanol.

[0052] Two or more filters (e.g., 2 to 8) may be used, in which case the filter materials and / or pore sizes may be the same or different. Furthermore, circulation filtration may be performed in which the liquid to be purified is passed through the same filter more than once. In this case, circulation filtration may be performed using all or some of the filters used to filter the liquid to be purified. The sequential use of two or more filters with different pore sizes is not particularly limited, but examples include a method in which multiple filter units containing filters are arranged along a pipeline through which the purified product is transported. In this case, if an attempt is made to maintain a constant flow rate per unit time of the purified product throughout the entire pipeline, filters with smaller pore sizes may be subjected to greater pressure than filters with larger pore sizes. In this case, it is preferable to arrange a pressure regulating valve, a damper, or the like between the filters to maintain a constant pressure on the filters with smaller pore sizes, or to arrange filter units containing the same filters in parallel along the pipeline to increase the filtration area.

[0053] The filter material is not particularly limited, and examples thereof include known materials for filters. Specific examples of resins include polyamides such as nylon (e.g., 6-nylon and 6,6-nylon), polyolefins such as polyethylene and polypropylene, polystyrene, polyimide, polyamideimide, poly(meth)acrylate, fluorine-based resins such as polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylenepropene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride, polyvinyl alcohol, polyester, cellulose, and cellulose acetate. Among these, at least one selected from the group consisting of nylon (especially 6,6-nylon), polyolefin (especially polypropylene or polyethylene), poly(meth)acrylate, and fluorine-based resin (especially polytetrafluoroethylene (PTFE) or perfluoroalkoxyalkane (PFA)) is preferred, as it has better solvent resistance and the resulting chemical solution has better defect suppression performance. These polymers can be used alone or in combination of two or more. In addition to resin, materials such as diatomaceous earth and glass may also be used. Alternatively, the filter material may be a polymer (such as nylon-grafted UPE) in which polyamide (e.g., nylons such as nylon-6 or nylon-6,6) is graft-copolymerized onto polyolefin (such as UPE (ultra-high molecular weight polyethylene) described below).

[0054] The filter may also be a surface-treated filter. The surface treatment method is not particularly limited, and known methods can be used. Examples of surface treatment methods include chemical modification treatment, plasma treatment, hydrophobic treatment, coating, gas treatment, and sintering.

[0055] As the chemical modification treatment, a method of introducing ion exchange groups into the filter is preferred. That is, a filter having an ion exchange group may be used as the filter. Examples of the ion exchange group include a cation exchange group and an anion exchange group, and examples of the cation exchange group include a sulfonic acid group, a carboxyl group, and a phosphate group, while examples of the anion exchange group include a quaternary ammonium group. The method for introducing the ion exchange group into the filter is not particularly limited, but examples include a method of reacting a compound containing an ion exchange group and a polymerizable group with the filter (typically a grafting method).

[0056] The method for introducing ion exchange groups is not particularly limited, but may involve irradiating the filter with ionizing radiation (such as α-rays, β-rays, γ-rays, X-rays, and electron beams) to generate active moieties (radicals). After this irradiation, the filter is immersed in a monomer-containing solution to graft polymerize the monomer onto the filter. As a result, the polymer obtained by polymerization of the monomer is grafted onto the filter. The generated polymer can be contacted with a compound containing anion exchange groups or cation exchange groups to introduce ion exchange groups into the polymer.

[0057] The use of a filter having ion exchange groups makes it easy to control the content of metal particles and metal ions in the chemical solution within a desired range. The material constituting the filter having ion exchange groups is not particularly limited, but examples thereof include fluorine-based resins and materials in which ion exchange groups have been introduced into polyolefins, and materials in which ion exchange groups have been introduced into fluorine-based resins are more preferred. The pore size of the filter having an ion exchange group is not particularly limited, but is preferably 1 to 30 nm, more preferably 5 to 20 nm.

[0058] The filters used in the filtration step may be two or more filters made of different materials, for example, two or more filters selected from the group consisting of filters made of polyolefins, fluorine-based resins, polyamides, and filters made of these materials with ion exchange groups introduced therein.

[0059] The pore structure of the filter is not particularly limited and may be appropriately selected depending on the components in the product to be purified. In this specification, the pore structure of the filter refers to the pore size distribution, the positional distribution of pores in the filter, the shape of the pores, etc., and can typically be controlled by the filter manufacturing method. For example, porous membranes can be obtained by sintering powders of resin or the like, while fibrous membranes can be obtained by methods such as electrospinning, electroblowing, and meltblowing, each of which has a different pore structure.

[0060] By "porous membrane" is meant a membrane that retains components of a product to be purified, such as gels, particles, colloids, cells, and poly-oligomers, while allowing components substantially smaller than the pores to pass through the pores. The retention of components of a product by a porous membrane may depend on operating conditions, such as face velocity, the use of surfactants, pH, and combinations thereof, and may depend on the pore size and structure of the porous membrane and the size and structure of the particles to be removed (e.g., hard particles or gels).

[0061] The pore structure of a porous membrane (for example, a porous membrane containing UPE, PTFE, etc.) is not particularly limited, but examples of the shape of the pores include lace-like, string-like, and node-like. The pore size distribution in the porous membrane and the distribution of its positions within the membrane are not particularly limited. The size distribution may be narrower and the distribution positions within the membrane may be symmetrical. Alternatively, the size distribution may be wider and the distribution positions within the membrane may be asymmetrical (the above membrane is also referred to as an "asymmetric porous membrane"). In an asymmetric porous membrane, the pore size varies within the membrane, and typically, the pore size increases from one surface of the membrane to the other. In this case, the surface with more pores with larger pore sizes is referred to as the "open side," and the surface with more pores with smaller pore sizes is also referred to as the "tight side." Furthermore, examples of asymmetric porous membranes include membranes in which the size of the pores is smallest at a certain position within the thickness of the membrane (also called "hourglass-shaped" membranes).

[0062] It is also preferable to thoroughly wash the filter before use. When an unwashed filter (or a filter that has not been washed sufficiently) is used, impurities contained in the filter are likely to be carried into the chemical solution.

[0063] As described above, the filtration step according to the embodiment of the present invention may be a multi-stage filtration step in which the material to be purified is passed through two or more different types of filters. The different filters mean that the filters differ in at least one of pore size, pore structure, and material. The material to be purified may be passed through the same filter multiple times, or may be passed through multiple filters of the same type. In addition, in terms of ease of production of the chemical solution of the present invention, it is preferable to use a filter containing a fluororesin. Among them, the filter containing the fluororesin is preferably a multistage filter using a plurality of filters. As the filter containing the fluororesin, a filter having a pore size of 20 nm or less is preferred. In particular, in terms of ease of production of the chemical solution of the present invention, it is preferable to carry out a first filtration step in which the material to be purified is filtered using a filter with a pore size of 100 nm or more, and a second filtration step in which the material to be purified is filtered using a filter containing a fluorine-based resin (preferably a filter made of PTFE) with a pore size of 10 nm or less, in this order. In the first filtration step, coarse particles are removed.

[0064] The material of the liquid-contacting parts of the purification device used in the filtration process (meaning the inner wall surfaces that may come into contact with the purified material and the chemical solution) is not particularly limited, but it is preferable that they be made of at least one material selected from the group consisting of non-metallic materials (such as fluororesins) and electropolished metallic materials (such as stainless steel) (hereinafter, these will be collectively referred to as "corrosion-resistant materials").

[0065] The non-metallic material is not particularly limited, and may be any known material. Examples of non-metallic materials include at least one selected from the group consisting of polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, and fluorine-based resin (e.g., tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene-ethylene copolymer resin, trifluorochloroethylene-ethylene copolymer resin, vinylidene fluoride resin, trifluorochloroethylene copolymer resin, and vinyl fluoride resin).

[0066] The metal material is not particularly limited, and examples thereof include known materials. The metal material may be, for example, a metal material having a total chromium and nickel content of more than 25 mass% relative to the total mass of the metal material, and more preferably 30 mass% or more. There is no particular upper limit for the total chromium and nickel content in the metal material, but it is generally preferably 90 mass% or less. Metallic materials include, for example, stainless steel and nickel-chromium alloys.

[0067] The stainless steel is not particularly limited, and known stainless steels can be used. Among them, an alloy containing 8% or more by mass of nickel is preferred, and an austenitic stainless steel containing 8% or more by mass of nickel is more preferred. Examples of austenitic stainless steel include SUS (Steel Use Stainless) 304 (Ni content 8% by mass, Cr content 18% by mass), SUS304L (Ni content 9% by mass, Cr content 18% by mass), SUS316 (Ni content 10% by mass, Cr content 16% by mass), and SUS316L (Ni content 12% by mass, Cr content 16% by mass).

[0068] The nickel-chromium alloy is not particularly limited, and examples thereof include known nickel-chromium alloys, among which a nickel-chromium alloy having a nickel content of 40 to 75 mass % and a chromium content of 1 to 30 mass % is preferred. Examples of nickel-chromium alloys include Hastelloy (trade name, the same applies hereinafter), Monel (trade name, the same applies hereinafter), and Inconel (trade name, the same applies hereinafter). More specific examples include Hastelloy C-276 (Ni content 63 mass%, Cr content 16 mass%), Hastelloy-C (Ni content 60 mass%, Cr content 17 mass%), and Hastelloy C-22 (Ni content 61 mass%, Cr content 22 mass%). Furthermore, the nickel-chromium alloy may further contain boron, silicon, tungsten, molybdenum, copper, cobalt, and the like in addition to the above alloy, as required.

[0069] The method for electrolytically polishing a metal material is not particularly limited, and known methods can be used, such as those described in paragraphs

[0011] to

[0014] of JP 2015-227501 A and paragraphs

[0036] to

[0042] of JP 2008-264929 A.

[0070] It is believed that electrolytic polishing of metal materials results in a higher chromium content in the surface passive layer than in the parent phase, and therefore, it is believed that using a refining device with wetted parts made of electrolytically polished metal materials makes it difficult for metal particles to leak into the product being refined. The metal material may be buffed. The buffing method is not particularly limited, and known methods can be used. The size of the abrasive grains used for the buffing finish is not particularly limited, but #400 or smaller is preferred, as this tends to reduce the surface irregularities of the metal material. Buffing is preferably performed before electrolytic polishing.

[0071] It is preferable that the purification of the target substance, including the opening of containers, cleaning of containers and equipment, storage of solutions, and analysis, be all performed in a clean room. The clean room is preferably a clean room with a cleanliness level of Class 4 or higher as defined by the international standard ISO14644-1:2015 established by the International Organization for Standardization. Specifically, it is preferable that the clean room meets any of ISO Class 1, ISO Class 2, ISO Class 3, and ISO Class 4, more preferably ISO Class 1 or ISO Class 2, and even more preferably ISO Class 1.

[0072] One preferred embodiment of the method for producing a drug solution of the present invention includes a production method comprising, in this order: a step of distilling a cyclohexanone-containing purified product to obtain a distilled purified product; a first filtration step of filtering the distilled purified product using a filter having a pore size of 100 nm or more; and a second filtration step of filtering the purified product obtained in the first filtration step using a filter containing a fluorine-based resin (preferably a filter made of PTFE) having a pore size of 10 nm or less.

[0073] <Medicine container> The liquid medicine may be stored in a container until use. Such a container and the liquid medicine stored in the container are collectively referred to as a liquid medicine container. The liquid medicine is taken out of the stored liquid medicine container and used.

[0074] As a container for storing the above-mentioned chemical solution, a container that is highly clean inside and that elutes little impurities is preferred for use in semiconductor device manufacturing. There are no particular limitations on the containers that can be used, but examples include the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd.

[0075] As the container, it is also preferable to use a multi-layer bottle whose inner wall has a six-layer structure made of six types of resin, or a multi-layer bottle whose inner wall has a seven-layer structure made of six types of resin, in order to prevent impurities from being mixed in (contaminated) with the drug solution. Examples of such containers include the container described in JP 2015-123351 A.

[0076] The liquid-contacting portion in the container that comes into contact with the chemical solution may be made of the corrosion-resistant material already described (preferably electrolytically polished stainless steel or a fluororesin such as PFA) or glass. In terms of achieving a more effective effect of the present invention, it is preferable that 90% or more of the area of ​​the liquid-contacting portion is made of the above material, and it is more preferable that the entire liquid-contacting portion is made of the above material.

[0077] The porosity of the container of the drug solution container is preferably 0.5 to 35% by volume, and more preferably 1 to 20% by volume. That is, in the method for producing a drug solution container of the present invention, it is preferable to carry out the containing step of containing the obtained drug solution in the container so that the porosity of the container is 0.5 to 35% by volume. The porosity is calculated according to formula (1). Formula (1): Porosity = {1 - (Volume of the drug solution in the container / Volume of the container)} x 100 The container volume is synonymous with the internal volume (capacity) of the container. By setting the porosity within this range, contamination such as impurities can be limited, thereby ensuring storage stability.

[0078] <Chemical use> The chemical solution of the present invention is used as a pre-wetting solution. In particular, the chemical liquid of the present invention is preferably a pre-wet liquid used in the manufacture of semiconductor devices (preferably semiconductor chips). Prewetting is a process in which, for example, when a specific liquid (preferably, an actinic ray-sensitive or radiation-sensitive resin composition used to form a resist film for obtaining a resist pattern, as described below) is to be applied to the surface (preferably, on the substrate) of a workpiece (preferably, a substrate), another liquid (prewetting liquid) is applied immediately before the specific liquid is applied to the workpiece, thereby making it easier to apply the specific liquid uniformly on the surface of the workpiece. In other words, the chemical solution of the present invention is preferably a pre-wet solution that is applied to a substrate before the actinic ray-sensitive or radiation-sensitive resin composition is applied to form a resist film on the substrate.

[0079] The chemical solution of the present invention is preferably used as a pre-wet solution when forming a resist pattern. A preferred embodiment of using the chemical solution of the present invention is to use the chemical solution as a pre-wet solution in a method of forming a resist pattern having the following steps 1 to 4 in order. Process 1: Applying chemicals to the substrate (pre-wetting process) Step 2: A step of applying an actinic ray-sensitive or radiation-sensitive resin composition onto a substrate to form a coating film (resist film) (resist film forming step). Step 3: Exposing the coating film (resist film) to light Step 4: A step of developing the exposed resist film using a developer to obtain a resist pattern (development step) Steps 1 to 4 will be described in detail below.

[0080] (Process 1) Step 1 is a step (pre-wetting step) in which a chemical solution is applied onto a substrate. The method for applying the chemical solution onto the substrate is not particularly limited, and spin coating is particularly preferred. The type of substrate is not particularly limited, and examples thereof include a silicon substrate and a silicon substrate coated with silicon dioxide. An anti-reflection film or the like may be formed on the substrate.

[0081] (Process 2) Step 2 is a step (resist film formation step) of applying an actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as a "resist composition") onto a substrate to form a coating film (resist film) on the substrate. As a coating method for coating the resist composition onto a predetermined substrate, spin coating is preferred. There are no particular restrictions on the thickness of the resist film, but a thickness of 10 to 200 nm is preferred in order to enable the formation of a fine resist pattern with higher precision.

[0082] The resist composition preferably contains a resin (acid-decomposable resin) (hereinafter also referred to as "resin P") having a group that decomposes under the action of acid to generate a polar group. As the resin P, a resin having a repeating unit represented by formula (AI) described below, which is a resin whose solubility in a developer containing an organic solvent as the main component decreases under the action of acid, is more preferred. The resin having a repeating unit represented by formula (AI) described below has a group that decomposes under the action of acid to generate an alkali-soluble group (hereinafter also referred to as "acid-decomposable group"). Examples of the polar group include an alkali-soluble group, such as a carboxy group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a phenolic hydroxyl group, and a sulfo group.

[0083] In the acid-decomposable group, the polar group is protected by a group that is detached by an acid (acid-detachable group). Examples of the acid-detachable group include -C(R 36 )(R 37 )(R 38 ), -C(R 36)(R 37 )(OR 39 ), and -C(R 01 )(R 02 )(OR 39 ) are listed.

[0084] In the formula, R 36 ~R 39 R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 36 and R 37 may be bonded to each other to form a ring.

[0085] R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0086] Resin P preferably contains a repeating unit represented by formula (AI).

[0087] [ka]

[0088] In formula (AI), Xa1 represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. Ra1 to Ra3 each independently represent an alkyl group (straight-chain or branched) or a cycloalkyl group (monocyclic or polycyclic). Two of Ra1 to Ra3 may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

[0089] Examples of the alkyl group represented by Xa1, which may have a substituent, include a methyl group and -CH2-R 11 Examples of such groups include groups represented by R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Xa1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

[0090] Examples of the divalent linking group for T include an alkylene group, a -COO-Rt- group, and a -O-Rt- group, where Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0091] The alkyl groups Ra1 to Ra3 are preferably alkyl groups having 1 to 4 carbon atoms.

[0092] The cycloalkyl groups of Ra1 to Ra3 are preferably monocyclic cycloalkyl groups such as a cyclopentyl group or a cyclohexyl group, or polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The cycloalkyl group formed by combining two of Ra1 to Ra3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

[0093] The cycloalkyl group formed by combining two of Ra1 to Ra3 may have, for example, one of the methylene groups constituting the ring replaced with a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group.

[0094] In the repeating unit represented by formula (AI), for example, Ra1 is a methyl group or an ethyl group, and Ra2 and Ra3 are bonded to form the above-mentioned cycloalkyl group.

[0095] Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxy group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms), and a substituent having 8 or less carbon atoms is preferred.

[0096] The content of the repeating unit represented by formula (AI) is preferably from 20 to 90 mol %, more preferably from 25 to 85 mol %, and even more preferably from 30 to 80 mol %, based on all repeating units in the resin P.

[0097] Furthermore, the resin P preferably contains a repeating unit Q having a lactone structure. The repeating unit Q having a lactone structure preferably has a lactone structure in the side chain, and more preferably is a repeating unit derived from a (meth)acrylic acid derivative monomer. The repeating unit Q having a lactone structure may be used alone or in combination of two or more kinds, but it is preferred to use one kind alone. The content of the repeating unit Q having a lactone structure relative to all repeating units in the resin P is preferably from 3 to 80 mol %, more preferably from 3 to 60 mol %.

[0098] The lactone structure is preferably a 5- to 7-membered lactone structure, and more preferably a structure in which another ring structure is condensed with the 5- to 7-membered lactone structure to form a bicyclo structure or a spiro structure. The lactone structure preferably has a repeating unit having a lactone structure represented by any one of the following formulas (LC1-1) to (LC1-17): The lactone structure is preferably a lactone structure represented by formula (LC1-1), formula (LC1-4), formula (LC1-5), or formula (LC1-8), and more preferably a lactone structure represented by formula (LC1-4).

[0099] [ka]

[0100] The lactone structure portion may have a substituent (Rb2). Preferred examples of the substituent (Rb2) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxy group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or greater, multiple substituents (Rb2) may be the same or different, and multiple substituents (Rb2) may be bonded to each other to form a ring.

[0101] Resin P may further contain a repeating unit containing an organic group having a polar group, in particular a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. The alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group, a diamantyl group, or a norbornane group, and the polar group is preferably a hydroxyl group or a cyano group.

[0102] When the resin P contains a repeating unit containing an organic group having a polar group, the content thereof is preferably 1 to 50 mol %, more preferably 1 to 30 mol %, and even more preferably 5 to 25 mol %, based on the total repeating units in the resin P.

[0103] Resin P is preferably a resin comprising a repeating unit selected from the group consisting of a repeating unit represented by formula (a), a repeating unit represented by formula (b), a repeating unit represented by formula (c), a repeating unit represented by formula (d), and a repeating unit represented by formula (e).

[0104] [ka]

[0105] R x1 ~R x5 each independently represents a hydrogen atom or an alkyl group which may have a substituent. R1 to R4 each independently represent a monovalent substituent, and p1 to p4 each independently represent 0 or a positive integer. R a represents a linear or branched alkyl group. T1 to T5 each independently represent a single bond or a divalent linking group. R5 represents a monovalent organic group. a to e represent mole percent, and each independently represents a number within the ranges 0≦a≦100, 0≦b≦100, 0≦c<100, 0≦d<100, and 0≦e<100, provided that a+b+c+d+e=100 and a+b≠0. However, the repeating unit (e) has a structure different from any of the repeating units (a) to (d).

[0106] R x1 ~R x5 Examples of the alkyl group represented by the formula (I) which may have a substituent include a methyl group and -CH-R 11 Examples of such groups include groups represented by R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. R x1 ~R x5 are each independently preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

[0107] Examples of the divalent linking groups represented by T1 to T5 include alkylene groups, -COO-Rt- groups, and -O-Rt- groups, where Rt represents an alkylene group or a cycloalkylene group. Each of T1 to T5 is preferably independently a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0108] R a represents a linear or branched alkyl group. Examples include a methyl group, an ethyl group, and a t-butyl group. Among these, a linear or branched alkyl group having 1 to 4 carbon atoms is preferred. R1 to R4 each independently represent a monovalent substituent. Examples of R1 to R4 include, but are not limited to, a hydroxyl group, a cyano group, and a linear or branched alkyl or cycloalkyl group having a hydroxyl or cyano group. p1 to p4 each independently represent 0 or a positive integer, and the upper limit of p1 to p4 corresponds to the number of hydrogen atoms that can be substituted in each repeating unit. R5 represents a monovalent organic group. R5 is not particularly limited, but examples thereof include monovalent organic groups having a sultone structure, monovalent organic groups having a cyclic ether such as tetrahydrofuran, dioxane, 1,4-thioxane, dioxolane, and 2,4,6-trioxabicyclo[3.3.0]octane, and acid-decomposable groups (e.g., adamantyl groups quaternized by substituting an alkyl group for the carbon atom bonding to the -COO group).

[0109] The repeating unit (b) is also preferably formed from a monomer described in paragraphs 0014 to 0018 of JP-A No. 2016-138219.

[0110] a to e represent mole percent, and each independently represents a number within the ranges 0≦a≦100, 0≦b≦100, 0≦c<100, 0≦d<100, and 0≦e<100, provided that a+b+c+d+e=100 and a+b≠0.

[0111] a+b is preferably from 20 to 90 mol %, more preferably from 25 to 85 mol %, and even more preferably from 30 to 80 mol %. Furthermore, c+d (the content of repeating units having a lactone structure relative to all repeating units) is preferably from 3 to 80 mol %, more preferably from 3 to 60 mol %.

[0112] The weight average molecular weight of the resin P is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, as determined by GPC (gel permeation chromatography) in terms of polystyrene. In the resist composition, the content of resin P is preferably from 50 to 99.9 mass % of the total solid content, and more preferably from 60 to 99.0 mass %.

[0113] The resist composition may contain components other than the resin P described above (for example, an acid generator, a basic compound, a quencher, a hydrophobic resin, a surfactant, a solvent, and the like). Any known components can be used as the other components. Examples of other components contained in the resist composition include components contained in actinic ray-sensitive or radiation-sensitive resin compositions described in JP 2013-195844 A, JP 2016-057645 A, JP 2015-207006 A, WO 2014 / 148241 A, JP 2016-188385 A, and JP 2017-219818 A.

[0114] (Step 3) Step 3 is a step of exposing the coating film (resist film) to light (exposure step). The type of actinic ray or radiation used for exposure is not particularly limited, but light with a wavelength of 250 nm or less is preferred, and examples thereof include KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F2 excimer laser light (157 nm), EUV light (13.5 nm), and electron beams. During the exposure, the exposure may be carried out through a mask, if necessary.

[0115] (Step 4) Step 3 is a step (developing step) in which the exposed coating film (resist film) is developed using a developer to form a resist pattern. Development methods include the dip method, in which the substrate is immersed in a tank filled with developer for a certain period of time; the puddle method, in which developer is piled up on the surface of the substrate by surface tension and left to stand for a certain period of time; the spray method, in which developer is sprayed onto the surface of the substrate; and the dynamic dispense method, in which developer is continuously dispensed onto a substrate that is rotating at a constant speed while a dispense nozzle is scanned at a constant speed. The development time is preferably from 10 to 300 seconds, more preferably from 20 to 120 seconds. The temperature of the developer is preferably from 0 to 50°C, more preferably from 15 to 35°C. As the developer, a known developer (organic solvent, alkaline aqueous solution, etc.) may be used. The developer may contain a surfactant, if necessary.

[0116] (Step 5) The method for forming a resist pattern may further include, after step 4, step 5 (rinsing step). Step 5 is a step of cleaning the resist pattern with a rinse liquid. Rinsing methods include a method in which the substrate is immersed in a tank filled with rinse liquid for a certain period of time (dip method), a method in which rinse liquid is piled up on the surface of the substrate by surface tension and left to stand for a certain period of time to develop (puddle method), a method in which rinse liquid is sprayed onto the surface of the substrate (spray method), and a method in which rinse liquid is continuously discharged by scanning a discharge nozzle at a constant speed onto a substrate that is rotating at a constant speed (dynamic dispense method). The rinsing time is preferably from 10 to 300 seconds, more preferably from 20 to 120 seconds. The temperature of the rinse liquid is preferably 0 to 50°C, more preferably 15 to 35°C. As the rinse liquid, a known rinse liquid (organic solvent, water, etc.) may be used.

[0117] The above-described resist pattern forming method is preferably applied to the manufacture of semiconductor chips. [Example]

[0118] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples. Unless otherwise specified, the terms "%", "ppm", "ppb", and "ppt" used in the tables shown later are intended to mean "% by mass", "ppm by mass", "ppb by mass", and "ppt by mass", respectively.

[0119] In addition, in preparing the chemical solutions in the Examples and Comparative Examples, handling of containers, preparation of chemical solutions, filling, storage, and analytical measurements were all carried out in a clean room meeting ISO class 2 or 1 standards.

[0120] [Production of chemical solutions] <Product to be purified> Cyclohexanones A to U were used as the substances to be purified to produce the chemical solutions of the Examples and Comparative Examples. Cyclohexanones A to U are cyclohexanones that differ in one or more conditions selected from the group consisting of manufacturer, storage period, material of the liquid-contacting part of the storage container, porosity of the container during storage, and storage temperature. The manufacturers selected were (1) Toyo Gosei, (2) Honeywell, (3) Ube Industries, (4) Showa Denko, (5) Fujifilm Ultra Pure Solutions, (6) Alfa Aeser, (7) Gore@, (8) Shiny, and (9) Fujifilm Electronic Materials USA. Semiconductor-grade cyclohexanone was purchased from each company. The storage period was 1 to 24 months. The materials of the liquid-contacting parts of the storage container were electrolytically polished stainless steel, non-electrolytically polished stainless steel, PTFE, or polyethylene. The porosity of the container during storage was set to 1 to 95% by volume. The storage temperature was 5 to 50°C. However, cyclohexanone E (raw material E) is cyclohexanone that has just been purchased from (9) Fujifilm Electronic Materials USA and has not been stored for a long time.

[0121] <Filling container> The following containers were used to store the drug solutions. EP-SUS: A vessel with electropolished stainless steel parts in contact with the liquid PFA: Container with liquid-contacting parts coated with perfluoroalkoxyalkane The void ratio of the chemical solution in each container is shown in Table 1.

[0122] <Purification procedure> One of the above-mentioned products to be purified was selected and subjected to the distillation purification treatment shown in Table 1. In the table, "Yes-1" in the "Distillation purification" column indicates that atmospheric distillation was carried out once using a distillation column (theoretical number of plates: 15). "Yes-2" indicates that vacuum distillation was carried out once using a distillation column (theoretical plate number: 25 plates). "Yes-3" indicates that vacuum distillation was carried out twice using a distillation column (theoretical plate number: 25 plates). "Yes-4" indicates that vacuum distillation was carried out once using a distillation column (theoretical plate number: 20 plates). "Yes-5" indicates that vacuum distillation was carried out twice using a distillation column (theoretical plate number: 20 plates). "Yes-6" indicates that vacuum distillation was carried out once using a distillation column (theoretical number of plates: 8). "Yes-7" indicates that atmospheric distillation was carried out once using a distillation column (theoretical number of plates: 25). "Yes-8" indicates that atmospheric distillation was carried out once using a distillation column (theoretical number of plates: 20). "Yes-9" indicates that atmospheric distillation was carried out twice using a distillation column (theoretical plate number: 30 plates). "Yes-10" indicates that atmospheric distillation was carried out twice using a distillation column (theoretical number of plates: 35). "No" indicates that no distillation was performed.

[0123] Next, the distilled and purified product was stored in a storage tank, and the product stored in the storage tank was filtered by passing it through filters 1 to 4 listed in Table 1 in this order, and then stored in a container. Next, as shown in Table 1 below, in Examples where the "First Circulation" column is marked with "Yes," a circulating filtration process was carried out in which the purified product stored in a container was filtered through filters 5 to 7 shown in Table 1, and the purified product after filtration through filter 7 was circulated upstream of filter 5 and filtered again through filters 5 to 7. After the circulating filtration process, the chemical solution was placed in the container. As shown in Table 1 below, in examples where the "First Circulation" column is marked "None," the above-mentioned circulation treatment was not carried out, and the purified product stored in the storage tank was filtered using filters 5 to 7 listed in Table 1. Next, as shown in Table 1 below, in Examples where the "Second Circulation" column is marked with "Yes," the resulting purified product was filtered through filter 8 shown in Table 1, and the purified product after filtration through filter 8 was circulated upstream of filter 8 and filtered again through filter 8, thereby carrying out a circulating filtration process. In addition, when the filter used for each filter is not specified, it means that filtration using that filter was not performed. For example, in Example 1, circulating filtration was performed using only filters 5 and 6. After filtration using filters 5 to 7 (and, if filtration using filter 8 was also performed, after filtration using filter 8), the product to be purified (chemical liquid) was first placed in a container, and then further placed in a container (filled container) shown in Table 1 with a void ratio (volume %) shown in Table 1.

[0124] (Filter) The following filters were used: "PP": Polypropylene filter, manufactured by Pall "IEX": Ion exchange resin filter, manufactured by Entegris PTFE: Polytetrafluoroethylene filter, manufactured by Entegris "Nylon": 6,6-nylon filter, manufactured by Pall PTFE: Polytetrafluoroethylene filter, manufactured by Entegris In Table 1, the diameter listed next to the material of the filter used indicates the pore size of the filter. For example, "PP 200nm" indicates that a filter made of polypropylene, manufactured by Pall Corporation, with a pore size of 200nm was used.

[0125] In addition, in the above-mentioned series of purification processes, the liquid-contacting parts of various devices (e.g., distillation columns, piping, storage tanks, containers, etc.) that come into contact with the product to be purified were made of electrolytically polished stainless steel unless otherwise specified.

[0126] [analysis] The contents of organic components and metal components in the chemical solution were measured by the following method.

[0127] <Organic ingredient content> The content of organic components in the chemical solution was measured using a gas chromatography mass spectrometer (GC / MS) (manufactured by Agilent, GC: 7890B, MS: 5977B EI / CI MSD).

[0128] <Metal component content> The content of metal components (metal ions, metal-containing particles) in the chemical solution was measured by a method using ICP-MS and SP-ICP-MS. The following equipment was used: Manufacturer: PerkinElmer Model: NexION350S The following analysis software was used for the analysis. ·Syngistix Nano Application Module for "SP-ICP-MS" Syngistix for ICP-MS software

[0129] [evaluation] The prepared drug solutions were evaluated by the following methods.

[0130] <Defect suppression (residue suppression)> The defect suppression performance of the chemical solution was evaluated by the following method. A resist pattern was formed by the following procedure. First, an organic anti-reflective coating composition ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied to a silicon substrate having a diameter of 300 mm and baked at 205° C. for 60 seconds to form an anti-reflective coating having a thickness of 78 nm. To improve the coating properties, a pre-wet liquid (each of the chemical solutions of the Examples or Comparative Examples was used) was dropped onto the surface of the silicon wafer on which the anti-reflection film had been formed, on the side of the anti-reflection film, and spin coating was carried out. Next, the prepared "actinic ray-sensitive or radiation-sensitive resin composition 1 (shown below)" was applied onto the anti-reflective film after the prewetting process, and prebaked (PB) at 100°C for 60 seconds to form a resist film with a thickness of 150 nm. The obtained wafer was scanned with an ArF excimer laser scanner (NA 0.75) at 25 mJ / cm 2 ], followed by pattern exposure. Then, the wafer was heated (PEB) at 120°C for 60 seconds. Then, development was performed by puddling with FETW butyl acetate for 30 seconds. Next, a negative resist pattern was formed by rotating the wafer at 4000 rpm for 30 seconds. The resulting negative resist pattern was then post-baked (POB) at 200°C for 300 seconds. Through the above process, an L / S resist pattern with a line / space ratio of 1:1 was obtained.

[0131] (Actinic ray-sensitive or radiation-sensitive resin composition 1) Acid-decomposable resin (resin represented by the following formula (weight average molecular weight (Mw): 7500): the numerical value shown for each repeating unit means mol %): 100 parts by mass

[0132] [ka]

[0133] Photoacid generator shown below: 8 parts by mass

[0134] [ka]

[0135] The quencher shown below: 5 parts by mass (the mass ratio, from left to right, was 0.1:0.3:0.3:0.2). Of the quenchers listed below, the polymer type has a weight-average molecular weight (Mw) of 5,000. The numerical values ​​listed for each repeating unit indicate the molar ratio.

[0136] [ka]

[0137] Hydrophobic resin shown below: 4 parts by mass (the mass ratio, from left to right, was 0.5:0.5). Of the hydrophobic resins shown below, the hydrophobic resin on the left has a weight average molecular weight (Mw) of 7000, and the hydrophobic resin on the right has a weight average molecular weight (Mw) of 8000. In each hydrophobic resin, the numerical value written for each repeating unit means the molar ratio. [ka]

[0138] solvent: PGMEA (propylene glycol monomethyl ether acetate): 3 parts by mass Cyclohexanone: 600 parts by mass γ-BL (γ-butyrolactone): 100 parts by mass

[0139] Using a pattern defect measurement device (Hitachi High-Technologies Corporation, Multipurpose SEM (Scanning Electron Microscope) "Inspago" RS6000 series), the number of defects due to residues left behind during development on the resist patterns of the wafers on which the resist patterns were formed as described above was measured. The number of defects due to the residues measured during development was used to evaluate the defect suppression (residue suppression) according to the following criteria.

[0140] "A": The number of defects was 100 or less per wafer. "B": The number of defects was more than 100 / wafer but less than 200 / wafer. "C": The number of defects was more than 200 / wafer but less than 300 / wafer. "D": The number of defects was more than 300 / wafer but less than 400 / wafer. "E": The number of defects was more than 400 / wafer but less than 500 / wafer. "F": The number of defects exceeded 500 per wafer.

[0141] <Evaluation over time> The chemical solution was stored for one year at 30° C. Thereafter, the above test (evaluation of defect suppression ability) was carried out using the stored chemical solution, and evaluation was performed according to the following criteria. "A": The difference between the number of defects using the chemical solution before storage (number of defects based on residues during development) and the number of defects using the chemical solution after storage (number of defects using the chemical solution after storage - number of defects using the chemical solution before storage) is less than 3.0% based on the number of defects using the chemical solution before storage. "B": The difference between the number of defects using the chemical solution before storage and the number of defects using the chemical solution after storage (number of defects using the chemical solution after storage - number of defects using the chemical solution before storage) is 3.0% or more but less than 5.0% of the number of defects using the chemical solution before storage. "C": The difference between the number of defects using the chemical solution before storage and the number of defects using the chemical solution after storage (number of defects using the chemical solution after storage - number of defects using the chemical solution before storage) is 5.0% or more, based on the number of defects using the chemical solution before storage.

[0142] <Resist composition performance> Each of the chemical solutions from the Examples and Comparative Examples was applied as a pre-wet solution to a silicon substrate with a diameter of 300 mm, and then Fujifilm Electronics Corporation's Resist 4415 (resist composition) was applied in varying amounts between 0.4 and 0.2 ml to form a resist film. The thickness of each of the resist films thus obtained was measured, and the amount of resist composition applied when the in-plane thickness uniformity of the resist film was 3% or less was determined. The smaller the amount of resist composition applied when the in-plane thickness uniformity of the resist film was 3% or less, the better the chemical-saving performance of the resist composition can be determined.

[0143] "A": With an application amount of 0.20 ml, the in-plane uniformity of the resist film thickness was 3% or less. "B": When the application amount was more than 0.20 ml and not more than 0.25 ml, the in-plane film thickness uniformity of the resist film was 3% or less. "C": When the application amount was more than 0.25 ml and not more than 0.30 ml, the in-plane film thickness uniformity of the resist film was 3% or less. "D": The in-plane thickness uniformity of the resist film was 3% or less when the application amount was more than 0.30 ml and not more than 0.40 ml. Or, even when the application amount was 0.40 ml, the in-plane thickness uniformity of the resist film did not reach 3% or less.

[0144] [result] Table 1 shows the manufacturing method of the chemical solution, the analysis results, and the evaluation results for each example or comparative example.

[0145] In Table 1, the column labeled "Ratio X (X: integer of 1 to 10)" indicates the mass ratio of the content of each component listed next to the ratio X in the chemical solution. For example, the column "Ratio 1 Formula 1 Compound / Formula 2 Compound" indicates the mass ratio of the content of the Formula 1 compound to the content of the Formula 2 compound in the drug solution (mass content of the Formula 1 compound / mass content of the Formula 2 compound). The "Total Amount (ppt)" column in the "Metal Components" column indicates the total content of one or more metal components selected from the group consisting of particulate metal components and ionic metal components. The column "Fe particles (ppt)" indicates the content of particulate metal components containing Fe and having a particle size of 15 to 20 nm relative to the total mass of the chemical solution. The column "Pd particles (ppt)" indicates the content of particulate metal components containing Pd and having a particle size of 15 to 20 nm relative to the total mass of the chemical solution. The column "High boiling point organic compounds" indicates the content of high boiling point organic compounds other than cyclohexanone derivatives and having a boiling point of 450°C or higher relative to the total mass of the chemical solution. The column "Number of requirements satisfied" indicates the number of requirements 1 to 19 that the chemical solution of each example satisfied.

[0146] Requirement 1: The content of the compound of formula 1 relative to the total mass of the chemical solution is 0.01 to 70 ppm by mass. Requirement 2: The total content of the first compounds relative to the total mass of the chemical solution is 0.005 to 95 ppm by mass. Requirement 3: In the drug solution, the mass ratio of the content of the compound of formula 1 to the content of the compound of formula 2 (content of the compound of formula 1 / content of the compound of formula 2) is 1-500. Requirement 4: In the drug solution, the mass ratio of the content of the compound of formula 1 to the content of the compound of formula 3 (content of the compound of formula 1 / content of the compound of formula 3) is 1 to 3,000. Requirement 5: In the drug solution, the mass ratio of the content of the compound of formula 2 to the content of the compound of formula 3 (content of the compound of formula 2 / content of the compound of formula 3) is 1-150. Requirement 6: The total content of hydroxycyclohexanones relative to the total mass of the chemical solution is 0.001 to 1000 ppm by mass. Requirement 7: In the chemical solution, the mass ratio of the content of 2-hydroxycyclohexanone to the content of 3-hydroxycyclohexanone (content of 2-hydroxycyclohexanone / content of 3-hydroxycyclohexanone) is 0.005 to 300. Requirement 8: In the chemical solution, the mass ratio of the content of 2-hydroxycyclohexanone to the content of 4-hydroxycyclohexanone (content of 2-hydroxycyclohexanone / content of 4-hydroxycyclohexanone) is 0.01 to 15. Requirement 9: In the chemical solution, the mass ratio of the content of 3-hydroxycyclohexanone to the content of 4-hydroxycyclohexanone (content of 3-hydroxycyclohexanone / content of 4-hydroxycyclohexanone) is 0.003 to 100. Requirement 10: The content of 1,2-cyclohexanedione relative to the total mass of the chemical solution is 0.0005 to 40 ppm by mass. Requirement 11: The content of cyclohexanol relative to the total mass of the chemical solution is 0.0003 to 30 ppm by mass. Requirement 12: The content of 1-hexanoic acid relative to the total mass of the chemical solution is 5 to 600 ppm by mass. Requirement 13: In the chemical solution, the mass ratio of the content of 1,2-cyclohexanedione to the content of cyclohexanol (1,2-cyclohexanedione content / cyclohexanol content) is 0.2 to 400. Requirement 14: In the chemical solution, the mass ratio of the content of 1,2-cyclohexanedione to the content of 1-hexanoic acid (content of 1,2-cyclohexanedione / content of 1-hexanoic acid) is 0.005 to 5. Requirement 15: In the chemical solution, the mass ratio of the content of cyclohexanol to the content of 1-hexanoic acid (content of cyclohexanol / content of 1-hexanoic acid) is 0.0005 to 0.5. Requirement 16: The total content of the second compounds relative to the total mass of the chemical solution is 0.5 to 10 ppm by mass. Requirement 17: The total content of metal components relative to the total mass of the chemical solution is 10 to 350 mass ppt. Requirement 18: In the chemical solution, the mass ratio of the content of metal particles containing Fe and having a particle size of 15 to 20 nm to the content of metal particles containing Pd and having a particle size of 15 to 20 nm (content of metal particles containing Fe and having a particle size of 15 to 20 nm / content of metal particles containing Pd and having a particle size of 15 to 20 nm) is 1 to 23. Requirement 19: The total content of high-boiling organic compounds relative to the total mass of the chemical solution is 10 to 1000 mass ppb.

[0147] [Table 1]

[0148] [Table 2]

[0149] [Table 3]

[0150] [Table 4]

[0151] [Table 5]

[0152] From the results shown in the table, it was confirmed that when the chemical solution of the present invention was used as a pre-wet solution, it was excellent in terms of defect suppression.

[0153] In particular, it was confirmed that the greater the number of requirements 1 to 19 that were satisfied, the more excellent the effects of the present invention in the drug solution.

Claims

1. Cyclohexanone and A chemical solution containing one or more first compounds selected from the group consisting of a compound represented by general formula (1), a compound represented by general formula (2), and a compound represented by general formula (3), and water, The content of the cyclohexanone is 98.000 to 99.999% by mass relative to the total mass of the chemical solution, the total content of the first compound is 0.001 to 100 ppm by mass relative to the total mass of the chemical solution; The content of the water is 1 to 500 ppm by mass relative to the total mass of the chemical solution, A chemical liquid used as a pre-wet liquid. 【Chemistry 1】

2. The chemical solution according to claim 1, wherein the content of the compound represented by the general formula (1) in the chemical solution is 0.01 to 70 ppm by mass with respect to the total mass of the chemical solution.

3. The chemical solution according to claim 1 or 2, wherein the total content of the first compound in the chemical solution is 0.005 to 95 ppm by mass with respect to the total mass of the chemical solution.

4. The chemical solution according to any one of claims 1 to 3, wherein the mass ratio of the content of the compound represented by the general formula (1) to the content of the compound represented by the general formula (2) in the chemical solution is 1 to 500.

5. The chemical solution according to any one of claims 1 to 4, wherein the mass ratio of the content of the compound represented by the general formula (1) to the content of the compound represented by the general formula (3) in the chemical solution is 1 to 3000.

6. The chemical solution according to any one of claims 1 to 5, wherein the mass ratio of the content of the compound represented by the general formula (2) to the content of the compound represented by the general formula (3) in the chemical solution is 1 to 150.

7. Further, the composition contains one or more hydroxycyclohexanones selected from the group consisting of 2-hydroxycyclohexanone, 3-hydroxycyclohexanone, and 4-hydroxycyclohexanone, The chemical solution according to any one of claims 1 to 6, wherein the total content of the hydroxycyclohexanone is 0.001 to 1000 ppm by mass relative to the total mass of the chemical solution.

8. 8. The chemical solution according to claim 7, wherein the mass ratio of the content of 2-hydroxycyclohexanone to the content of 3-hydroxycyclohexanone in the chemical solution is 0.005 to 300.

9. 9. The chemical solution according to claim 7, wherein the mass ratio of the content of 2-hydroxycyclohexanone to the content of 4-hydroxycyclohexanone in the chemical solution is 0.01 to 15.

10. The chemical solution according to any one of claims 7 to 9, wherein the mass ratio of the content of 3-hydroxycyclohexanone to the content of 4-hydroxycyclohexanone in the chemical solution is 0.003 to 100.

11. Further, it contains 1,2-cyclohexanedione, The chemical solution according to any one of claims 1 to 10, wherein the content of 1,2-cyclohexanedione is 0.0005 to 40 ppm by mass relative to the total mass of the chemical solution.

12. Further, it contains cyclohexanol, The chemical solution according to any one of claims 1 to 11, wherein the content of cyclohexanol is 0.0003 to 30 ppm by mass relative to the total mass of the chemical solution.

13. Further, it contains 1-hexanoic acid, The chemical solution according to any one of claims 1 to 12, wherein the content of 1-hexanoic acid is 5 to 600 ppm by mass relative to the total mass of the chemical solution.

14. Contains 1,2-cyclohexanedione and cyclohexanol, The chemical solution according to any one of claims 1 to 13, wherein the mass ratio of the content of 1,2-cyclohexanedione to the content of cyclohexanol in the chemical solution is 0.2 to 400.

15. Contains 1,2-cyclohexanedione and 1-hexanoic acid, The chemical solution according to any one of claims 1 to 14, wherein the mass ratio of the content of 1,2-cyclohexanedione to the content of 1-hexanoic acid in the chemical solution is 0.005 to 5.

16. Contains cyclohexanol and 1-hexanoic acid, The chemical solution according to any one of claims 1 to 15, wherein the mass ratio of the content of cyclohexanol to the content of 1-hexanoic acid in the chemical solution is 0.0005 to 0.

5.

17. Further, the composition contains one or more second compounds selected from the group consisting of compounds represented by general formula (4) and compounds represented by general formula (5), The chemical solution according to any one of claims 1 to 16, wherein the total content of the second compounds is 0.5 to 10 ppm by mass with respect to the total mass of the chemical solution. 【Chemistry 2】

18. Further, it contains a high-boiling organic compound having a boiling point of 450°C or higher, The chemical solution according to any one of claims 1 to 17, wherein the content of the high-boiling organic compound is 10 to 1000 mass ppb relative to the total mass of the chemical solution.

19. Further, the composition contains one or more metal components selected from the group consisting of particulate metal components and ionic metal components, The chemical solution according to any one of claims 1 to 18, wherein the total content of the metal components is 10 to 350 mass ppt with respect to the total mass of the chemical solution.

20. The metal component contains a particulate metal component containing Fe and having a particle size of 15 to 20 nm, and a particulate metal component containing Pd and having a particle size of 15 to 20 nm, The chemical solution according to claim 19, wherein the mass ratio of the content of the particulate metal component containing Fe and having a particle size of 15 to 20 nm to the content of the particulate metal component containing Pd and having a particle size of 15 to 20 nm in the chemical solution is 1 to 23.

21. A substrate on which an actinic ray-sensitive or radiation-sensitive resin composition is applied to form a resist film, The chemical solution according to any one of claims 1 to 20, which is a pre-wet liquid that is applied onto the substrate before the actinic ray-sensitive or radiation-sensitive resin composition is applied.

22. a pre-wetting step of applying the chemical solution according to claim 21 onto the substrate; a step of applying the actinic ray-sensitive or radiation-sensitive resin composition onto the substrate that has been subjected to the prewetting step to form a resist film; exposing the resist film to light; and developing the exposed resist film with a developer to obtain a resist pattern.

23. A method for manufacturing a semiconductor chip, comprising the method for forming a resist pattern according to claim 22.

24. A drug solution container containing a container and the drug solution according to any one of claims 1 to 21 contained in the container, A chemical solution container, wherein a liquid-contacting portion that comes into contact with the chemical solution in the container is formed of electropolished stainless steel or fluorine-based resin.

25. 25. The drug solution container according to claim 24, wherein the void ratio within the container calculated by formula (1) is 1 to 20% by volume. Equation (1): Porosity = {1 - (volume of the chemical solution in the container / container volume of the container)} x 100

26. A method for producing a chemical solution according to any one of claims 1 to 21, wherein a material to be purified containing cyclohexanone is purified to obtain the chemical solution, A method for producing a chemical solution, comprising a distillation step of distilling the product to be purified.

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