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

Abstract

The invention provides a chemical solution, a chemical solution container, a method for forming a resist pattern, and a method for manufacturing a semiconductor chip. When the chemical solution is used as a developing solution or a rinsing solution, the chemical solution can form the resist pattern with suppressed variation of pattern intervals. The liquid medicine contains n-butyl acetate and isobutyl acetate, the content of the n-butyl acetate in the liquid medicine is 99.000-99.999% by mass relative to the total mass of the liquid medicine, and the content of the isobutyl acetate in the liquid medicine is 1.0-1000 ppm by mass relative to the total mass of the liquid medicine.

Description

[0001] This application is a divisional application of the application number 201980064889.0 filed by the applicant and the invention title is “Drug solution, drug solution container, resist pattern forming method, semiconductor chip manufacturing method”. The filing date of the parent case of this application is September 4, 2019, and the priority date is October 3, 2018. Technical Field

[0002] The present invention relates to a drug solution, a drug solution container, a resist pattern forming method and a method for manufacturing a semiconductor chip. Background Art

[0003] When a semiconductor device is manufactured by a wiring formation process including photolithography, a chemical solution containing water and / or an organic solvent is used as a processing liquid such as a developer and a rinser.

[0004] As a liquid chemical used for conventional resist pattern formation, Patent Document 1 discloses a "method for producing an organic treatment liquid for pattern formation of a chemically amplified resist film capable of reducing particle generation in pattern formation technology (paragraph

[0010] )". Patent Document 1 discloses a method of using the organic treatment liquid as a developer or a rinser.

[0005] Previous technical literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2015-084122 Summary of the invention

[0008] Technical issues to be solved by the invention

[0009] On the other hand, in recent years, miniaturization has been progressing along with the advancement of photolithography technology, and further high-definition resist patterns used when manufacturing semiconductor devices have been required.

[0010] As a result of forming a resist pattern using n-butyl acetate specifically described in Patent Document 1, the inventors found that the spacing between patterns of the formed resist pattern has a large deviation relative to the current required level, and further improvement is needed. In addition, the spacing between patterns refers to the spacing between linear patterns when a plurality of linear patterns are formed.

[0011] An object of the present invention is to provide a chemical solution which, when used as a developer or a rinser, can form a resist pattern with suppressed variation in pattern intervals.

[0012] Furthermore, another object of the present invention is to provide a chemical solution container, a resist pattern forming method, and a method for manufacturing a semiconductor chip.

[0013] Means for solving technical problems

[0014] The present inventors have conducted intensive studies to solve the above problems and have found that the above problems can be solved by the following structure.

[0015] (1) A liquid medicine containing n-butyl acetate and isobutyl acetate, wherein:

[0016] The content of n-butyl acetate is 99.000 to 99.999% by mass relative to the total mass of the liquid medicine.

[0017] The content of isobutyl acetate is 1.0 to 1000 ppm by mass relative to the total mass of the chemical solution.

[0018] (2) The drug solution according to (1), further comprising amyl acetate,

[0019] The content of amyl acetate is 1.0 to 300 ppm by mass based on the total mass of the chemical solution.

[0020] (3) The chemical solution according to (2), wherein the amyl acetate contains a compound selected from the group consisting of 1-methylbutyl acetate, 2-methylbutyl acetate, and 3-methylbutyl acetate.

[0021] (4) The drug solution according to (2) or (3), wherein the mass ratio of the content of isobutyl acetate to the content of amyl acetates is 0.5 to 300.

[0022] (5) The drug solution according to any one of (1) to (4), further comprising butyl propionate,

[0023] The content of butyl propionate is 1.0 to 700 ppm by mass relative to the total mass of the chemical solution.

[0024] (6) The drug solution according to (5), further comprising amyl acetate,

[0025] The mass ratio of the content of butyl propionate to the content of amyl acetate is 0.10 to 10.0.

[0026] (7) The drug solution according to any one of (1) to (6), further comprising butyl formate.

[0027] The content of butyl formate is 1.0 to 50 ppm by mass relative to the total mass of the chemical solution.

[0028] (8) The drug solution according to any one of (1) to (7), further comprising dibutyl ether,

[0029] The content of dibutyl ether is 5.0 to 500 ppm by mass relative to the total mass of the chemical solution.

[0030] (9) The drug solution according to (8), further comprising amyl acetate,

[0031] The mass ratio of the content of dibutyl ether to the content of amyl acetates is more than 0.5 and is 35.0 or less.

[0032] (10) The drug solution according to any one of (1) to (9), further comprising 1-butanol,

[0033] The content of 1-butanol is 5.0 to 3500 ppm by mass relative to the total mass of the chemical solution.

[0034] (11) The drug solution according to any one of (1) to (10), further comprising a sulfate group.

[0035] The content of sulfate radical is 1.0 to 200 ppm by mass relative to the total mass of the chemical solution.

[0036] (12) The drug solution according to (11), further comprising amyl acetate,

[0037] The mass ratio of the content of sulfate radical to the content of amyl acetate is 0.01 to 10.0.

[0038] (13) The drug solution according to any one of (1) to (12), further comprising a metal component,

[0039] The content of the metal component is 0.01 to 150 ppt by mass relative to the total mass of the chemical solution.

[0040] (14) The chemical solution according to (13), wherein the mass ratio of the content of isobutyl acetate to the content of the metal component is 10 4 ~10 7 .

[0041] (15) The drug solution according to any one of (1) to (13), further comprising sulfate and a metal component.

[0042] The mass ratio of sulfate content to metal content is 10 4 ~10 8 .

[0043] (16) The chemical solution according to any one of (1) to (15), which is used as a developer or rinser.

[0044] (17) A drug solution container comprising a container and the drug solution according to any one of (1) to (16) contained in the container.

[0045] (18) The drug solution container according to (17), wherein the liquid contact portion that contacts the drug solution in the container is formed of electropolished stainless steel or fluorine-based resin.

[0046] (19) The drug solution container according to (17) or (18), wherein the porosity in the container determined by the formula (1) described below is 5 to 30% by volume.

[0047] (20) A method for forming a resist pattern, comprising:

[0048] A step of forming a coating film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition;

[0049] A process of exposing the coating film;

[0050] The step of developing the exposed coating film with a developer to form a resist pattern,

[0051] In the resist pattern forming method, the developer is the chemical solution described in any one of (1) to (16).

[0052] (21) A method for forming a resist pattern, comprising:

[0053] A step of forming a coating film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition;

[0054] A process of exposing the coating film;

[0055] A step of developing the exposed coating film using a developer to form a resist pattern; and

[0056] The process of cleaning the resist pattern using a rinse solution.

[0057] In the resist pattern forming method, the rinse liquid is the chemical solution described in any one of (1) to (16).

[0058] (22) A method for manufacturing a semiconductor chip, comprising the resist pattern forming method described in (20) or (21).

[0059] (23) A liquid medicine containing n-butyl acetate and isobutyl acetate, wherein:

[0060] The content of n-butyl acetate is 99.000 to 99.999% by mass relative to the total mass of the liquid medicine.

[0061] The content of isobutyl acetate is 1.0 to 1000 ppm by mass relative to the total mass of the chemical solution.

[0062] The liquid medicine also contains metal components.

[0063] The content of the metal component is 0.01 to 100 ppt by mass relative to the total mass of the chemical solution.

[0064] (24) A liquid medicine containing n-butyl acetate and isobutyl acetate, wherein:

[0065] The content of n-butyl acetate is 99.000 to 99.999% by mass relative to the total mass of the liquid medicine.

[0066] The content of isobutyl acetate is 1.0 to 1000 ppm by mass relative to the total mass of the chemical solution.

[0067] The drug solution also contains amyl acetate, butyl propionate, 1-butanol, butyl formate and dibutyl ether.

[0068] The content of amyl acetate is 0.1 to 4000 ppm by mass relative to the total mass of the drug solution.

[0069] The content of butyl propionate is 0.1 to 4000 ppm by mass relative to the total mass of the drug solution.

[0070] The content of 1-butanol is 0.1 to 4000 ppm by mass relative to the total mass of the liquid medicine.

[0071] The content of butyl formate is 0.1 to 4000 ppm by mass relative to the total mass of the chemical solution.

[0072] The content of dibutyl ether is 0.1 to 4000 ppm by mass relative to the total mass of the chemical solution.

[0073] (25) A method for manufacturing a drug solution container, the drug solution container comprising a container and the drug solution described in (1), the method comprising:

[0074] A process of distilling a purified product containing n-butyl acetate (preferably a solution containing n-butyl acetate, isobutyl acetate, and other components other than n-butyl acetate and isobutyl acetate) to obtain a distilled purified product; a first filtering process of filtering the distilled purified product using a filter having a pore size of 100 nm or more; a second filtering process of filtering the purified product obtained in the first filtering process using a filter containing a fluorine-based resin having a pore size of 10 nm or less to obtain a drug solution; and a containing process of containing the obtained drug solution in a container in such a manner that the porosity in the container determined by the formula (1) described later becomes 2 to 35% by volume.

[0075] (26) A drug solution container comprising a container and the drug solution described in (1), wherein:

[0076] The liquid contact portion in contact with the chemical solution in the container is formed of electropolished stainless steel or fluorine-based resin, and the porosity in the container determined by the formula (1) described below is 2 to 35% by volume.

[0077] (27) A method for forming a resist pattern, comprising:

[0078] A step of forming a coating film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition;

[0079] The process of exposing the coating film to light; and

[0080] The step of developing the exposed coating film with a developer to form a resist pattern,

[0081] In the resist pattern forming method,

[0082] The actinic ray-sensitive or radiation-sensitive resin composition contains a resin comprising a repeating unit selected from the group consisting of a repeating unit represented by the formula (a) described below, a repeating unit represented by the formula (b) described below, a repeating unit represented by the formula (c) described below, a repeating unit represented by the formula (d) described below, and a repeating unit represented by the formula (e) described below,

[0083] The developer is the solution described in (1).

[0084] (28) A method for forming a resist pattern, comprising:

[0085] A step of forming a coating film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition;

[0086] A process of exposing the coating film;

[0087] A step of developing the exposed coating film using a developer to form a resist pattern; and

[0088] The process of cleaning the resist pattern using a rinse solution.

[0089] In the resist pattern forming method, the developer is the chemical solution described in (1),

[0090] The flushing liquid is n-butyl acetate.

[0091] Effects of the Invention

[0092] According to the present invention, it is possible to provide a chemical solution which, when used as a developer or a rinser, can form a resist pattern with suppressed variation in pattern intervals.

[0093] Furthermore, according to the present invention, a chemical solution container, a resist pattern forming method, and a method for manufacturing a semiconductor chip can be provided. DETAILED DESCRIPTION

[0094] Hereinafter, the present invention will be described in detail.

[0095] The description of the constituent requirements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0096] In addition, in this specification, the numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0097] In addition, in the present invention, "ppm" means "parts-per-million (10 -6 )”, “ppt” means “parts-per-trillion (10 -12 )”.

[0098] Furthermore, in the marking of the group (atomic group) in the present invention, the marking not marked with substitution and the marking not marked with substitution include not only the group without substitution but also the group containing substitution within the scope of not damaging the effect of the present invention. For example, the so-called "hydrocarbon group" includes not only the hydrocarbon group without substitution (unsubstituted hydrocarbon group) but also the hydrocarbon group containing substitution (substituted hydrocarbon group). In this respect, it is the same for each compound.

[0099] Furthermore, the "radiation" in the present invention refers to, for example, far ultraviolet rays, extreme ultraviolet rays (EUV), X-rays, or electron beams. Furthermore, the light in the present invention refers to actinic rays or radiation. The "exposure" in the present invention includes not only exposure using far ultraviolet rays, X-rays, or EUV, but also drawing using particle beams such as electron beams or ion beams, unless otherwise specified.

[0100] As a result of studying the properties of n-butyl acetate, the inventors of the present invention found that the deviation of the pattern spacing is suppressed by using n-butyl acetate and a specified amount of isobutyl acetate in combination. Although the detailed reason why the effect of the present invention can be obtained is not clear, it is believed that by using a specified amount of isobutyl acetate, the solubility of the coating in the liquid medicine is improved, the dissolution residue of the coating is suppressed, and as a result, the deviation of the pattern spacing is suppressed. It is speculated that this is because: from the viewpoint of the structural similarity between n-butyl acetate and isobutyl acetate, the dissolution ability of n-butyl acetate is not hindered, and the components with poor solubility in n-butyl acetate are dissolved by isobutyl acetate. In addition, as will be confirmed later, even in the case where the liquid medicine contains a specified amount of amyl acetate, butyl propionate, butyl formate or dibutyl ether, a more excellent effect can be obtained. It is believed that this is because: like isobutyl acetate, due to the structural similarity between these components and n-butyl acetate, the dissolution ability of n-butyl acetate is not hindered, and the characteristics as a liquid medicine are improved.

[0101] The chemical solution of the present invention (hereinafter, also simply referred to as "chemical solution") contains n-butyl acetate and isobutyl acetate.

[0102] Hereinafter, the components contained in the medicinal solution of the present invention will be described in detail.

[0103] <n-Butyl Acetate>

[0104] The drug solution contains n-butyl acetate. n-butyl acetate is a compound represented by the following structural formula.

[0105] [Chemical formula 1]

[0106]

[0107] The content of n-butyl acetate in the chemical solution is 99.000 to 99.999 mass % relative to the total mass of the chemical solution, preferably 99.500 to 99.995 mass %, more preferably 99.700 to 99.990 mass %, and still more preferably 99.900 to 99.990 mass %, from the viewpoint of further suppressing the deviation of the pattern interval (hereinafter also referred to as "the viewpoint of more excellent effect of the present invention").

[0108] <Isobutyl acetate>

[0109] The drug solution contains isobutyl acetate. Isobutyl acetate is a compound represented by the following structural formula.

[0110] [Chemical formula 2]

[0111]

[0112] The content of isobutyl acetate in the drug solution is 1.0 to 1000 ppm by mass relative to the total mass of the drug solution, preferably 10 to 950 ppm by mass, more preferably 100 to 950 ppm by mass, and even more preferably 300 to 950 ppm by mass, from the viewpoint of achieving more excellent effects of the present invention.

[0113] The chemical solution may contain other components in addition to n-butyl acetate and isobutyl acetate.

[0114] Other components are described below in detail.

[0115] <Amyl acetate>

[0116] The drug solution may contain amyl acetate. Amyl acetate refers to a compound in which R in the following structural formula is an alkyl group having 5 carbon atoms. The alkyl group may be linear or branched.

[0117] [Chemical formula 3]

[0118]

[0119] More specifically, examples of the amyl acetates include 1-methylbutyl acetate, 2-methylbutyl acetate, 3-methylbutyl acetate, 1,1-dimethylpropyl acetate, 2,2-dimethylpropyl acetate, and n-amyl acetate.

[0120] Among them, from the viewpoint of achieving more excellent effects of the present invention, the amyl acetate preferably contains at least one selected from the group consisting of 1-methylbutyl acetate, 2-methylbutyl acetate, and 3-methylbutyl acetate.

[0121] The content of amyl acetate in the drug solution is not particularly limited, and may be, for example, 0.1 to 4000 ppm by mass, usually 0.1 to 2000 ppm by mass, and preferably 1.0 to 300 ppm by mass, more preferably 1.0 to 250 ppm by mass, relative to the total mass of the drug solution, from the viewpoint of achieving a more excellent effect of the present invention.

[0122] When a plurality of compounds are contained in the drug solution as amyl acetates, the total amount thereof is preferably within the above range.

[0123] The mass ratio of the content of isobutyl acetate to the content of amyl acetates is not particularly limited, and may be, for example, 0.10 to 500.0, and is preferably 0.5 to 300 from the viewpoint of achieving more excellent effects of the present invention.

[0124] <Butyl Propionate>

[0125] The drug solution may contain butyl propionate. Butyl propionate is a compound represented by the following structural formula.

[0126] [Chemical formula 4]

[0127]

[0128] The content of butyl propionate in the drug solution is not particularly limited, and may be, for example, 0.1 to 4000 mass ppm, usually 0.1 to 2000 mass ppm, and preferably 1.0 to 700 mass ppm, more preferably 1.0 to 650 mass ppm, relative to the total mass of the drug solution, from the viewpoint of achieving a better effect of the present invention.

[0129] The mass ratio of the content of butyl propionate to the content of amyl acetates is not particularly limited, and may be, for example, 0.01 to 20.00, and is preferably 0.10 to 10.0 from the viewpoint of achieving more excellent effects of the present invention.

[0130] <Butyl formate>

[0131] The drug solution may contain butyl formate. Butyl formate is a compound represented by the following structural formula.

[0132] [Chemical formula 5]

[0133]

[0134] The content of butyl formate in the liquid medicine is not particularly limited, and is, for example, 0.1 to 4000 ppm by mass, usually 0.1 to 100 ppm by mass, and preferably 1.0 to 50 ppm by mass, more preferably 1.0 to 48 ppm by mass, relative to the total mass of the liquid medicine in order to achieve a better effect of the present invention.

[0135] <Dibutyl ether>

[0136] The drug solution may contain dibutyl ether. Dibutyl ether is a compound represented by the following structural formula.

[0137] [Chemical formula 6]

[0138]

[0139] The content of dibutyl ether in the drug solution is not particularly limited, and is, for example, 0.1 to 4000 mass ppm, usually 0.1 to 3500 mass ppm, and preferably 5.0 to 500 mass ppm based on the total mass of the drug solution from the viewpoint of achieving better effects of the present invention.

[0140] The mass ratio of the content of dibutyl ether to the content of amyl acetates is not particularly limited, and may be, for example, 0.10 to 50.0. From the viewpoint of further improving the effect of the present invention, it is preferably more than 0.5 and 35.0 or less.

[0141] <1-Butanol>

[0142] The drug solution may contain 1-butanol.

[0143] The content of 1-butanol in the drug solution is not particularly limited, and may be, for example, 0.1 to 4000 ppm by mass. From the viewpoint of achieving more excellent effects of the present invention, it is preferably 5.0 to 3500 ppm by mass, and more preferably 5 to 3000 ppm by mass, relative to the total mass of the drug solution.

[0144] <Sulfate>

[0145] The solution may contain sulfate (SO4 2- ).

[0146] The content of sulfate in the drug solution is not particularly limited, and is, for example, 0.1 to 500 ppm by mass. From the viewpoint of achieving more excellent effects of the present invention, it is preferably 1.0 to 200 ppm by mass, and more preferably 1.5 to 150 ppm by mass, relative to the total mass of the drug solution.

[0147] The mass ratio of the content of the sulfate radical to the content of the amyl acetate is not particularly limited, and may be, for example, 0.01 to 15.0, and is preferably 0.01 to 10.0 from the viewpoint of achieving more excellent effects of the present invention.

[0148] <Metal component>

[0149] The liquid medicine may contain metal components.

[0150] In the present invention, examples of the metal component include metal particles and metal ions. For example, the content of the metal component refers to the total content of the metal particles and the metal ions.

[0151] The chemical solution may contain either metal particles or metal ions, or both.

[0152] Examples of the metal elements in the metal component include Na (sodium), K (potassium), Ca (calcium), Fe (iron), Cu (copper), Mg (magnesium), Mn (manganese), Li (lithium), Al (aluminum), Cr (chromium), Ni (nickel), Ti (titanium) and Zr (zirconium). The metal component may contain one metal element or two or more metal elements.

[0153] The metal particles may be a single substance or an alloy.

[0154] The metal component may be a metal component inevitably contained in each component (raw material) contained in the chemical solution, a metal component inevitably contained during the production, storage and / or transfer of the chemical solution, or may be intentionally added.

[0155] When the chemical solution contains a metal component, the content thereof is not particularly limited, and may be 0.01 to 500 ppt by mass relative to the total mass of the chemical solution, and preferably 0.01 to 150 ppt by mass, from the viewpoint of achieving a more excellent effect of the present invention.

[0156] From the viewpoint of achieving more excellent effects of the present invention, when the chemical solution contains metal ions, the content thereof is preferably 0.01 to 200 ppt by mass, more preferably 0.01 to 100 ppt by mass, and further preferably 0.01 to 60 ppt by mass, based on the total mass of the chemical solution.

[0157] From the viewpoint of achieving more excellent effects of the present invention, when the chemical solution contains metal particles, the content thereof is preferably 0.01 to 200 ppt by mass, more preferably 0.01 to 100 ppt by mass, and even more preferably 0.01 to 40 ppt by mass relative to the total mass of the chemical solution.

[0158] The mass ratio of the content of isobutyl acetate to the content of the metal component is not particularly limited, and may be 10 3 ~108 From the viewpoint of more excellent effects of the present invention, preferably 10 4 ~10 7 .

[0159] The mass ratio of the content of sulfate radical to the content of metal component is not particularly limited, and can be 10 3 ~10 9 From the viewpoint of more excellent effects of the present invention, preferably 10 4 ~10 8 .

[0160] In addition, the types and contents of metal ions and metal particles in the chemical solution can be measured by SP-ICP-MS (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry).

[0161] Here, the SP-ICP-MS method uses the same apparatus as the general ICP-MS method (inductively coupled plasma mass spectrometry), and only the data analysis is different. The data analysis of the SP-ICP-MS method can be performed using commercially available software.

[0162] In the ICP-MS method, the content of the metal component to be measured is measured regardless of its existence form. Therefore, the total mass of the metal particles and metal ions to be measured is quantified as the content of the metal component.

[0163] On the other hand, the SP-ICP-MS method can measure the content of metal particles. Therefore, if the content of metal particles is subtracted from the content of metal components in the sample, the content of metal ions in the sample can be calculated.

[0164] As an apparatus for the SP-ICP-MS method, for example, Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry: inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200) manufactured by Agilent Technologies can be cited, and the measurement can be performed by the method described in the embodiment. As other apparatuses besides the above, in addition to NexION 350S manufactured by PerkinElmer, Agilent 8900 manufactured by Agilent Technologies can also be used.

[0165] In addition to the above, the medical solution may contain water.

[0166] <Method for producing liquid medicine>

[0167] The method for producing the above-mentioned drug solution is not particularly limited, and a known production method may be used.

[0168] For example, a prescribed amount of isobutyl acetate can be added to n-butyl acetate to produce a drug solution, or a commercial product can be purchased and purified to produce a drug solution. Among them, as a method for producing a drug solution, at least one method including a process of distilling the purified product (distillation process) and a process of filtering the purified product (filtration process) can be cited. In addition, as a purified product, a commercial n-butyl acetate solution can be cited. Commercial products usually contain impurities, for example, sometimes contain excessive isobutyl acetate and other impurities.

[0169] Hereinafter, the sequence of the above-mentioned distillation step and filtration step will be described in detail.

[0170] (Distillation process)

[0171] The distillation step is a step of distilling a purified product (a solution containing n-butyl acetate and isobutyl acetate. For example, a solution containing n-butyl acetate, isobutyl acetate, and other components other than n-butyl acetate and isobutyl acetate) to obtain a distilled purified product. The components removed by the distillation step are not particularly limited, but for example, isobutyl acetate, amyl acetates, butyl propionate, 1-butanol, butyl formate, sulfate, and water can be mentioned.

[0172] The method for distilling the product to be purified is not particularly limited, and a known method can be used. Typically, a method is exemplified in which a distillation column is disposed on the primary side of a purification device to be used in the filtration step described below, and the distilled product to be purified is introduced into a production tank.

[0173] In this case, the liquid contact portion of the distillation column is not particularly limited, but is preferably formed of a corrosion-resistant material described later.

[0174] In the distillation step, the material to be purified may be passed through the same distillation tower a plurality of times, or may be passed through different distillation towers. When the material to be purified is passed through different distillation towers, for example, a method in which a crude distillation treatment such as passing the material to be purified through a distillation tower to remove low-boiling components is performed, and then a rectification treatment such as passing through a distillation tower different from the crude distillation treatment to remove other components is performed.

[0175] Examples of the distillation tower include a plate type distillation tower and a vacuum plate type distillation tower.

[0176] Furthermore, in order to achieve both thermal stability during distillation and purification accuracy, reduced pressure distillation may be performed.

[0177] (Filtration process)

[0178] The filtration step is a step of filtering the above-mentioned purified substance using a filter.

[0179] The method of filtering the substance to be purified using the filter is not particularly limited, but it is preferred that the substance to be purified be passed (flow) through a filter unit having a housing and a filter element accommodated in the housing under pressure or without pressure.

[0180] The pore diameter of the filter is not particularly limited, and a filter having a pore diameter that is usually used for filtering a purified substance can be used. Among them, the pore diameter of the filter is preferably less than 200 nm, more preferably less than 20 nm, and further preferably less than 10 nm. The lower limit is not particularly limited, but from the viewpoint of productivity, it is usually preferably more than 1 nm.

[0181] In addition, in this specification, the pore diameter of the filter means the pore diameter determined by the bubble point of isopropyl alcohol.

[0182] There is no particular limitation on the method of sequentially using two or more filters with different pore diameters, but a method of disposing a plurality of filter units containing filters along the pipeline for transferring the purified material can be cited. In this case, if the flow rate per unit time of the purified material is to be set constant as the pipeline as a whole, a greater pressure may be applied to the filter with a smaller pore diameter than to the filter with a larger pore diameter. In this case, it is preferred to dispose a pressure regulating valve and a damper between the filters to set the pressure applied to the filter with a small pore diameter to be constant, or to dispose filter units containing the same filters side by side along the pipeline to increase the filtration area.

[0183] The material of the filter is not particularly limited, and known materials can be cited as the material of the filter. Specifically, in the case of resin, polyamides such as nylon (e.g., 6-nylon and 6,6-nylon); polyolefins such as polyethylene and polypropylene; polystyrene; polyimide; polyamide-imide; poly(meth)acrylate; fluorine-based resins such as polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride; polyvinyl alcohol; polyester; cellulose; cellulose acetate, etc.

[0184] Among them, from the viewpoint of having better solvent resistance and better defect suppression performance of the obtained chemical solution, at least one selected from the group consisting of nylon (preferably 6,6-nylon), polyolefin (preferably polyethylene), poly(meth)acrylate and fluorine resin (preferably polytetrafluoroethylene (PTFE) or perfluoroalkoxyalkane (PFA)). These polymers can be used alone or in combination of two or more.

[0185] Furthermore, other than the resin, diatomaceous earth, glass, etc. may also be used.

[0186] In addition, a polymer (nylon grafted UPE, etc.) obtained by graft-copolymerizing a polyamide (for example, nylon-6 or nylon-6,6) with a polyolefin (UPE (ultra-high molecular weight polyethylene) described later, etc.) can also be used as a filter material.

[0187] Furthermore, the filter may be a surface-treated filter. The surface treatment method is not particularly limited, and a known method can be used. Examples of the surface treatment method include chemical modification treatment, plasma treatment, hydrophobic treatment, coating, gas treatment, and sintering.

[0188] As the chemical modification treatment, a method of introducing an ion exchange group into the filter is preferred.

[0189] That is, as the filter, a filter having an ion exchange group can be used.

[0190] As the ion exchange group, a cation exchange group and an anion exchange group can be cited, as the cation exchange group, a sulfonic acid group, a carboxyl group and a phosphate group can be cited, as the anion exchange group, a quaternary ammonium group can be cited. The method of introducing the ion exchange group into the filter is not particularly limited, but a method of reacting a compound containing an ion exchange group and a polymerizable group with the filter (typically a method of grafting) can be cited.

[0191] The method for introducing the ion exchange group is not particularly limited, but the filter is irradiated with ionizing radiation (α-rays, β-rays, γ-rays, X-rays, electron beams, etc.) to generate active parts (free radicals). The irradiated filter is immersed in a solution containing monomers to graft polymerize the monomers on the filter. As a result, the polymer obtained by polymerizing the monomers is grafted on the filter. The generated polymer is contacted with a compound containing an anion exchange group or a cation exchange group to introduce the ion exchange group into the polymer.

[0192] If a filter having an ion exchange group is used, it is easier to control the content of metal particles and metal ions in the drug solution within a desired range. The material constituting the filter having an ion exchange group is not particularly limited, but materials in which the ion exchange group is introduced into a fluorine-based resin and a polyolefin can be cited, and materials in which the ion exchange group is introduced into a fluorine-based resin are more preferred.

[0193] The pore diameter 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.

[0194] As the filter used in the filtration step, two or more filters made of different materials may be used. For example, two or more filters selected from the group consisting of polyolefins, fluorine-based resins, polyamides, and materials into which ion exchange groups are introduced may be used.

[0195] The pore structure of the filter is not particularly limited and can be appropriately selected according to the components in the purified material. In this specification, the pore structure of the filter refers to the pore diameter distribution, the position distribution of the pores in the filter, and the shape of the pores, etc., which can typically be controlled by the manufacturing method of the filter.

[0196] For example, a porous membrane can be obtained by sintering a powder of a resin or the like, and a fiber membrane can be obtained by forming the membrane by electrospinning, electroblowing, meltblowing, etc. These have different pore structures.

[0197] "Porous membrane" refers to a membrane that retains components in the purified material such as gel, particles, colloids, cells and oligomers, but allows components substantially smaller than the pores to pass through the pores. Sometimes, the retention of components in the purified material based on the porous membrane depends on the operating conditions (for example, surface velocity, use of surfactants, pH and combinations thereof), and may depend on the pore size and structure of the porous membrane and the size and structure of the particles to be removed (hard particles or gels, etc.).

[0198] The pore structure of the porous membrane (for example, a porous membrane made of UPE, PTFE, etc.) is not particularly limited, and examples of the shape of the pores include lace-like, string-like, and node-like shapes.

[0199] The size distribution of the pores in the porous membrane and the position distribution in the membrane are not particularly limited. The size distribution can be smaller and the distribution position in the membrane is symmetrical. In addition, the size distribution can be larger and the distribution position in the membrane is asymmetric (the above-mentioned membrane is also referred to as "asymmetric porous membrane".). In an asymmetric porous membrane, the size of the pores changes in the membrane, and typically, the pore size increases from one surface of the membrane toward the other surface of the membrane. At this time, the surface of the side with more pores with a large pore size is referred to as the "open (open) side", and the surface of the side with more pores with a small pore size is referred to as the "dense (tite) side".

[0200] Furthermore, examples of asymmetric porous membranes include membranes in which the size of pores is the smallest at a certain position within the thickness of the membrane (this is also referred to as an "hourglass shape").

[0201] Furthermore, it is preferable to thoroughly clean the filter before use.

[0202] When an unwashed filter (or an insufficiently cleaned filter) is used, impurities contained in the filter are likely to enter the chemical solution.

[0203] As described above, the filtration step in the embodiment of the present invention may be a multi-stage filtration step in which the substance to be purified passes through two or more different filters. In addition, the different filters mentioned above refer to filters that are different in at least one of pore diameter, pore structure, and material.

[0204] Furthermore, the substance to be purified may be passed through the same filter multiple times, or may be passed through multiple filters of the same type.

[0205] Furthermore, from the viewpoint of facilitating the manufacture of the liquid medicine of the present invention, it is preferred to use a filter containing a fluorine resin. Among them, it is preferred to use a multi-stage filtration of a plurality of filters containing the above-mentioned fluorine resin. As the filter containing the above-mentioned fluorine resin, a filter having a pore diameter of 20 nm or less is preferred.

[0206] Among them, from the viewpoint of facilitating the manufacture of the liquid medicine of the present invention, it is preferred to sequentially carry out the following steps: a first filtering step, filtering the purified product using a filter having a pore size of 100 nm or more; and a second filtering step, filtering the purified product using a filter containing a fluorine resin having a pore size of 10 nm or less (preferably a filter made of PTFE). In the first filtering step, coarse particles are removed.

[0207] The material of the liquid contact part (referring to the inner wall surface that may come into contact with the purified material and the drug solution) of the purification device used in the filtration process is not particularly limited, but is preferably formed of at least one selected from the group consisting of non-metallic materials (fluorine-based resins, etc.) and electrolytically polished metal materials (stainless steel, etc.) (hereinafter, these are collectively referred to as "corrosion-resistant materials").

[0208] The non-metal material is not particularly limited, and known materials may be used.

[0209] As the non-metallic material, for example, at least one selected from the group consisting of polyethylene resin, polypropylene resin, polyethylene-polypropylene resin and fluorine-based resin (for example, tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene-ethylene copolymer resin, trifluorochloroethylene-ethylene copolymer resin, vinylidene fluoride resin, trifluorochloroethylene copolymer resin and vinyl fluoride resin, etc.) can be cited.

[0210] The metal material is not particularly limited, and known materials may be used.

[0211] As the metal material, for example, a metal material in which the total content of chromium and nickel exceeds 25% by mass relative to the total mass of the metal material can be cited, and more preferably 30% by mass or more. The upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but is generally preferably 90% by mass or less.

[0212] Examples of the metal material include stainless steel and nickel-chromium alloys.

[0213] Stainless steel is not particularly limited, and known stainless steel can be cited. Among them, preferably an alloy containing more than 8% by mass of nickel, more preferably an austenitic stainless steel containing more than 8% by mass of nickel. As austenitic stainless steel, for example, SUS (Steel Use Stainless: Steel Use Stainless Steel) 304 (Ni content is 8% by mass, Cr content is 18% by mass), SUS304L (Ni content is 9% by mass, Cr content is 18% by mass), SUS316 (Ni content is 10% by mass, Cr content is 16% by mass), and SUS316L (Ni content is 12% by mass, Cr content is 16% by mass), etc. can be cited.

[0214] The nickel-chromium alloy is not particularly limited, and known nickel-chromium alloys may be mentioned. Among them, nickel-chromium alloys having a nickel content of 40 to 75% by mass and a chromium content of 1 to 30% by mass are preferred.

[0215] Examples of nickel-chromium alloys include Hastelloy (trade name, the same below), Monel (trade name, the same below), and Inconel (trade name, the same below). More specifically, 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 %).

[0216] Furthermore, the nickel-chromium alloy may contain boron, silicon, tungsten, molybdenum, copper, cobalt, and the like in addition to the above-mentioned alloys as required.

[0217] The method for electrolytic polishing the metal material is not particularly limited, and a known method can be used. For example, the method described in paragraphs

[0011] to

[0014] of Japanese Patent Application Laid-Open No. 2015-227501 and paragraphs

[0036] to

[0042] of Japanese Patent Application Laid-Open No. 2008-264929 can be used.

[0218] Regarding the metal material, it is estimated that the chromium content in the surface passivation layer becomes higher than the chromium content in the parent phase due to electrolytic polishing. Therefore, it is estimated that when a purification device whose liquid contact part is formed of an electrolytically polished metal material is used, metal particles are less likely to flow into the purified liquid.

[0219] In addition, the metal material may also be polished. The polishing method is not particularly limited, and a known method can be used. The size of the abrasive grains used in fine polishing is not particularly limited, but from the viewpoint that the surface irregularities of the metal material are easily reduced, preferably #400 or less. In addition, polishing is preferably performed before electrolytic polishing.

[0220] Regarding the purification of the substance to be purified, it is preferred that the opening of the container attached thereto, the cleaning of the container and the device, the storage of the solution, and the analysis are all performed in a clean room. The clean room is preferably a clean room with a cleanliness level of Class 4 or higher as specified in the international standard ISO14644-1:2015 specified by the International Organization for Standardization. Specifically, it is preferred to satisfy any one of ISO Class 1, ISO Class 2, ISO Class 3, and ISO Class 4, more preferably satisfying ISO Class 1 or ISO Class 2, and even more preferably satisfying ISO Class 1.

[0221] As one of the preferred embodiments of the method for producing the drug solution of the present invention, there can be mentioned a method comprising the following steps in sequence: a step of distilling a substance to be purified containing n-butyl acetate (preferably a solution containing n-butyl acetate, isobutyl acetate, and other components other than n-butyl acetate and isobutyl acetate) to obtain a distilled substance to be purified; a first filtration step of filtering the distilled substance to be purified using a filter having a pore size of 100 nm or more; and a second filtration step of filtering the substance to be purified obtained in the first filtration step using a filter containing a fluorine-based resin having a pore size of 10 nm or less (preferably a filter made of PTFE).

[0222] <Drug Solution Container>

[0223] The above-mentioned drug solution can be contained in a container and stored until it is used. Such a container and the drug solution contained in the container are collectively referred to as a drug solution container. The drug solution is taken out from the stored drug solution container and then used.

[0224] As a container for storing the chemical solution, it is preferable that the cleanliness inside the container is high and the elution of impurities is small for the purpose of semiconductor device manufacturing.

[0225] The container that can be used is not particularly limited, and examples thereof include "Clean Bottle" series manufactured by AICELLO CHEMICAL CO., LTD. and "Pure Bottle" manufactured by KODAMA PLASTICS CO., LTD.

[0226] As the container, in order to prevent impurities from mixing into (contaminating) the drug solution, it is also preferable to use a multilayer bottle having a six-layer structure based on six kinds of resins or a multilayer bottle having a seven-layer structure based on six kinds of resins as the inner wall of the container. Examples of such containers include those described in Japanese Patent Application Laid-Open No. 2015-123351.

[0227] The liquid contact portion of the container may be the corrosion-resistant material described above (preferably electropolished stainless steel or fluorine resin) or glass. From the viewpoint of achieving a more excellent effect of the present invention, preferably 90% or more of the area of ​​the liquid contact portion is formed of the above material, and more preferably the entire liquid contact portion is formed of the above material.

[0228] The porosity of the drug solution container in the container is preferably 2 to 35% by volume, more preferably 5 to 30% by volume. That is, in the method for producing the drug solution container of the present invention, it is preferred to carry out a containing step of containing the obtained drug solution in the container so that the porosity in the container becomes 2 to 35% by volume.

[0229] In addition, the above-mentioned porosity is calculated according to formula (1).

[0230] Formula (1): Porosity = {1-(volume of the drug solution in the container / container volume of the container)}×100

[0231] The above-mentioned container volume has the same meaning as the internal volume (capacity) of the container.

[0232] By setting the porosity within this range, it is possible to ensure storage stability by limiting contamination by impurities and the like.

[0233] <Use of the liquid medicine>

[0234] The chemical solution of the present invention is preferably used in the production of semiconductor devices (preferably semiconductor chips).

[0235] Furthermore, the above-mentioned chemical solution can be used for purposes other than the production of semiconductor devices, and can also be used as a developer and rinser for polyimide, sensor resist, lens resist, and the like.

[0236] Furthermore, the above-mentioned liquid medicine can also be used as a solvent for medical purposes or cleaning purposes. For example, it can be applied to the cleaning of pipes, containers, and substrates (for example, wafers and glass, etc.).

[0237] As the cleaning application, it is also preferably used as a cleaning liquid (a pipe cleaning liquid, a container cleaning liquid, etc.) for cleaning pipes and containers that come into contact with the pre-wetting liquid or the like.

[0238] The chemical solution of the present invention is most preferably used as a developer or rinser when forming a resist pattern.

[0239] As a first preferred embodiment, there can be mentioned an embodiment in which the above-mentioned chemical solution is used as a developer in a resist pattern forming method including the following steps 1 to 3.

[0240] Step 1: Step of forming a coating film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition

[0241] Step 2: Exposure of the coating film

[0242] Step 3: Step of developing the exposed coating film using a developer to form a resist pattern

[0243] As a second preferred embodiment, there can be mentioned an embodiment in which the above-mentioned chemical solution is used as a rinse liquid in a resist pattern forming method including the following steps 1 to 4.

[0244] Step 1: Step of forming a coating film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition

[0245] Step 2: Exposure of the coating film

[0246] Step 3: Step of developing the exposed coating film using a developer to form a resist pattern

[0247] Step 4: Cleaning the resist pattern using a rinse solution

[0248] Hereinafter, steps 1 to 4 will be described in detail.

[0249] (Process 1)

[0250] Step 1 is a step of forming a coating film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition (hereinafter, also referred to as a "resist composition").

[0251] As a method of forming a coating film on a substrate using a resist composition, there is a method of applying the resist composition on a predetermined substrate. As a coating method, spin coating is preferred.

[0252] The thickness of the coating film is not particularly limited, but is preferably 10 to 200 nm from the viewpoint of being able to form a finer pattern with higher precision.

[0253] In addition, the type of the substrate is not particularly limited, and examples thereof include a silicon substrate and a silicon substrate coated with silicon dioxide.

[0254] The resist composition preferably contains a resin having a group that generates a polar group by decomposition by the action of an acid (acid-decomposable resin) (hereinafter also referred to as "resin P"). As the above-mentioned resin P, a resin whose solubility in a developer mainly composed of an organic solvent is reduced by the action of an acid, that is, a resin having a repeating unit represented by the formula (AI) described later is more preferably used. The resin having a repeating unit represented by the formula (AI) described later has a group that generates an alkali-soluble group by decomposition by the action of an acid (hereinafter also referred to as "acid-decomposable group").

[0255] Examples of the polar group include alkali-soluble groups, such as carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), phenolic hydroxyl groups, and sulfonic groups.

[0256] In the acid-decomposable group, the polar group is protected by a group that is detached by the action of 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 ).

[0257] 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 With R 37 They may be bonded to each other to form a ring.

[0258] 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.

[0259] The resin P preferably contains a repeating unit represented by the formula (AI).

[0260] [Chemical formula 7]

[0261]

[0262] In formula (AI),

[0263] Xa1 represents a hydrogen atom or an alkyl group which may have a substituent.

[0264] T represents a single bond or a divalent linking group.

[0265] Ra1 to Ra3 each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic).

[0266] Two of Ra1 to Ra3 may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

[0267] Examples of the alkyl group which may have a substituent represented by Xa1 include a methyl group and a -CH2-R 11 Represents a group. 11 It represents a halogen atom (fluorine atom or the like), a hydroxyl group or a monovalent organic group.

[0268] Xa1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

[0269] Examples of the divalent linking group for T include an alkylene group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group.

[0270] T is preferably a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH2- group, a -(CH2)2- group or a -(CH2)3- group.

[0271] As the alkyl group of Ra1 to Ra3, an alkyl group having 1 to 4 carbon atoms is preferred.

[0272] The cycloalkyl group for Ra1 to Ra3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecanyl, tetracyclododecyl or adamantyl.

[0273] The cycloalkyl group formed by bonding two of Ra1 to Ra3 is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

[0274] Regarding the cycloalkyl group formed by bonding two of Ra1 to Ra3, for example, one methylene group constituting the ring may be substituted with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group.

[0275] Regarding the repeating unit represented by the formula (AI), for example, it is preferred that Ra1 is a methyl group or an ethyl group, and Ra2 and Ra3 are bonded to form the above-mentioned cycloalkyl group.

[0276] Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms). Preferably, the substituent has 8 or less carbon atoms.

[0277] The content of the repeating unit represented by the formula (AI) is preferably 20 to 90 mol %, more preferably 25 to 85 mol %, and further preferably 30 to 80 mol % relative to all repeating units in the resin P.

[0278] Furthermore, the resin P preferably contains a repeating unit Q having a lactone structure.

[0279] The repeating unit Q having a lactone structure preferably has a lactone structure in a side chain, and is more preferably a repeating unit derived from a (meth)acrylic acid derivative monomer.

[0280] The repeating unit Q having a lactone structure may be used alone or in combination of two or more. However, it is preferred to use one alone.

[0281] The content of the repeating unit Q having a lactone structure is preferably 3 to 80 mol %, more preferably 3 to 60 mol %, based on all the repeating units in the resin P.

[0282] The lactone structure is preferably a 5- to 7-membered ring lactone structure, and more preferably a structure in which another ring structure is fused to a 5- to 7-membered ring lactone structure in the form of a bicyclic structure or a helical structure.

[0283] As the lactone structure, it is preferred to contain a repeating unit having a lactone structure represented by any one of the following formulas (LC1-1) to (LC1-17). As the lactone structure, it is preferred to contain 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).

[0284] [Chemical formula 8]

[0285]

[0286] The lactone structure part may have a substituent (Rb2). Preferred substituents (Rb2) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, carboxyl groups, halogen atoms, hydroxyl groups, cyano groups, and acid-decomposable groups. n2 represents an integer of 0 to 4. When n2 is 2 or more, multiple substituents (Rb2) may be the same or different, and multiple substituents (Rb2) may be bonded to each other to form a ring.

[0287] The resin P may further contain a repeating unit including an organic group having a polar group, in particular, a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group.

[0288] The alicyclic hydrocarbon structure substituted with a polar group is preferably adamantyl, diadamantyl or norbornyl. The polar group is preferably a hydroxyl group or a cyano group.

[0289] When the resin P contains repeating units containing an organic group having a polar group, the content thereof is preferably 1 to 50 mol % relative to all repeating units in the resin P, more preferably 1 to 30 mol %, and further preferably 5 to 25 mol %.

[0290] The resin P is preferably a resin containing 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).

[0291] [Chemical formula 9]

[0292]

[0293] R x1 ~R x5 Each independently represents a hydrogen atom or an alkyl group which may have a substituent.

[0294] R1 to R4 each independently represent a monovalent substituent, and p1 to p4 each independently represent 0 or a positive integer.

[0295] Ra represents a linear or branched alkyl group.

[0296] T1 to T5 each independently represent a single bond or a divalent linking group.

[0297] R5 represents a monovalent organic group.

[0298] a to e represent mol %, and each independently represents a number within the range of 0≤a≤100, 0≤b≤100, 0≤c<100, 0≤d<100, 0≤e<100. However, a+b+c+d+e=100, and a+b≠0.

[0299] The repeating unit (e) has a structure different from any of the repeating units (a) to (d).

[0300] As R x1 ~R x5 The alkyl group represented by the invention which may have a substituent includes, for example, a methyl group and a -CH2-R 11 Represents a group. 11 It represents a halogen atom (fluorine atom or the like), a hydroxyl group or a monovalent organic group.

[0301] R x1 ~R x5A hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group is each independently preferred.

[0302] Examples of the divalent linking group represented by T1 to T5 include an alkylene group, a -COO-Rt- group, and a -O-Rt- group, etc. In the formula, Rt represents an alkylene group or a cycloalkylene group.

[0303] T1 to T5 are each independently preferably a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH2- group, a -(CH2)2- group or a -(CH2)3- group.

[0304] Ra represents a linear or branched alkyl group. Examples thereof include a methyl group, an ethyl group, and a tert-butyl group. Among them, a linear or branched alkyl group having 1 to 4 carbon atoms is preferred.

[0305] R1 to R4 each independently represent a monovalent substituent. R1 to R4 are not particularly limited, and examples thereof include a hydroxyl group, a cyano group, and a linear or branched alkyl group or cycloalkyl group having a hydroxyl group or a cyano group.

[0306] p1 to p4 each independently represent 0 or a positive integer. The upper limit of p1 to p4 corresponds to the number of hydrogen atoms that can be substituted in each repeating unit.

[0307] R5 represents a monovalent organic group. R5 is not particularly limited, but examples thereof include a monovalent organic group having a sultone structure, a monovalent organic group having a cyclic ether such as tetrahydrofuran, dioxane, 1,4-thioxane, dioxolane, and 2,4,6-trioxabicyclo[3.3.0]octane, or an acid-decomposable group (for example, a quaternized adamantyl group in which the carbon at the position bonding to the -COO group is substituted with an alkyl group).

[0308] Furthermore, the repeating unit (b) is also preferably formed from a monomer described in paragraphs 0014 to 0018 of JP-A-2016-138219.

[0309] a to e represent mol %, and each independently represents a number within the range of 0≤a≤100, 0≤b≤100, 0≤c<100, 0≤d<100, 0≤e<100. However, a+b+c+d+e=100, and a+b≠0.

[0310] a+b (the content of repeating units having an acid-decomposable group relative to all repeating units) is preferably 20 to 90 mol %, more preferably 25 to 85 mol %, further preferably 30 to 80 mol %.

[0311] Furthermore, c+d (the content of the repeating unit having a lactone structure relative to all repeating units) is preferably 3 to 80 mol %, more preferably 3 to 60 mol %.

[0312] The weight average molecular weight of the resin P is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, as a polystyrene conversion value based on GPC (Gel permeation chromatography) method.

[0313] In the resist composition, the content of the resin P in the total solid content is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass.

[0314] The resist composition may contain other components (for example, an acid generator, a basic compound, a quencher, a hydrophobic resin, a surfactant, a solvent, etc.) in addition to the above-mentioned resin P.

[0315] As other components, any known components can be used. As other components contained in the resist composition, for example, components contained in the photosensitive or radiation-sensitive resin composition described in Japanese Patent Publication No. 2013-195844, Japanese Patent Publication No. 2016-057645, Japanese Patent Publication No. 2015-207006, International Publication No. 2014 / 148241, Japanese Patent Publication No. 2016-188385, and Japanese Patent Publication No. 2017-219818 can be cited.

[0316] (Process 2)

[0317] Step 2 is a step of exposing the coating film.

[0318] The types of actinic rays and radiation used for exposure are not particularly limited, but light with a wavelength of 250 nm or less is preferred, for example, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV light (13.5 nm) and electron beam.

[0319] During exposure, exposure can be performed through a mask as needed.

[0320] (Process 3)

[0321] Step 3 is a step of developing the exposed coating film using a developer to form a resist pattern.

[0322] As developing methods, there can be cited a method of immersing a substrate in a tank filled with a developer for a certain period of time (immersion method), a method of utilizing surface tension to deposit the developer on the surface of the substrate and allowing the developer to stand for a certain period of time for development (spin immersion method), a method of spraying the developer onto the surface of the substrate (spraying method), and a method of continuously spraying the developer while scanning a spray nozzle at a constant speed on a substrate rotating at a constant speed (dynamic distribution method).

[0323] The development time is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.

[0324] The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.

[0325] When the above-mentioned chemical solution is used as a developer, a surfactant may be contained in the developer as needed.

[0326] (Process 4)

[0327] Step 4 is a step of cleaning the resist pattern using a rinse liquid.

[0328] As the rinsing method, there can be cited a method of immersing the substrate in a tank filled with rinsing liquid for a certain period of time (immersion method), a method of utilizing surface tension to deposit the rinsing liquid on the surface of the substrate and letting it stand for a certain period of time for development (spin immersion method), a method of spraying the rinsing liquid on the surface of the substrate (spraying method), and a method of continuously spraying the rinsing liquid while scanning the spray nozzle at a constant speed on a substrate rotating at a constant speed (dynamic distribution method), etc.

[0329] The rinsing time is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.

[0330] The temperature of the rinse liquid is preferably 0 to 50°C, more preferably 15 to 35°C.

[0331] The first preferred embodiment includes steps 1 to 3 as described above, and may further include step 4. In this case, as the rinse solution used in step 4, the chemical solution of the present invention may be used, or other known solvents (eg, butyl acetate) may be used.

[0332] In the second preferred embodiment, steps 1 to 4 are included as described above, and the chemical solution of the present invention is used as the rinse solution. In the second preferred embodiment, the chemical solution of the present invention can be used as the developer used in step 3, or other known solvents (eg, butyl acetate) can be used.

[0333] The resist pattern forming method described above is preferably applied to the production of semiconductor chips.

[0334] Example

[0335] Below, the present invention is further described in detail based on embodiment.The materials, usage, ratio, processing content and processing sequence etc. shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention.Thereby, the scope of the present invention should not be interpreted in a limited manner by the embodiments shown below.

[0336] Furthermore, when preparing the chemical solutions of Examples and Comparative Examples, container handling, chemical solution preparation, filling, storage, and analysis and measurement were all performed in a clean room satisfying ISO Class 2 or 1.

[0337] (Filter)

[0338] As filters, the following filters were used.

[0339] PTFE500nm: Polytetrafluoroethylene filter, manufactured by Entegris, with a pore size of 500nm

[0340] PTFE 200nm: Polytetrafluoroethylene filter, manufactured by Entegris, with a pore size of 200nm

[0341] PTFE 100nm: Polytetrafluoroethylene filter, manufactured by Entegris, with a pore size of 100nm

[0342] PTFE 50nm: Polytetrafluoroethylene filter, manufactured by Entegris, with a pore size of 50nm

[0343] PTFE 20nm: Polytetrafluoroethylene filter, manufactured by Entegris, with a pore size of 20nm

[0344] PTFE 10nm: Polytetrafluoroethylene filter, manufactured by Entegris, with a pore size of 10nm

[0345] PTFE 5nm: Polytetrafluoroethylene filter, manufactured by Entegris, with a pore size of 5nm

[0346] "IEX": ion exchange resin filter, manufactured by Entegris, pore size 50 nm

[0347] "PP 200nm": Polypropylene filter, manufactured by Pall Corporation, pore size 200nm

[0348] "UPE 3nm": Ultra-high molecular weight polyethylene filter, manufactured by Pall Corporation, pore size 3nm

[0349] "Nylon 5nm": Nylon filter, manufactured by Pall Corporation, pore size 5nm

[0350] <Purified matter>

[0351] In order to prepare the chemical solutions of Examples and Comparative Examples, the following commercially available n-butyl acetate was used as a substance to be purified.

[0352] In addition, in the column of "Raw Materials" in Table 1, the manufacturers from which the purified substances used in Examples and Comparative Examples were purchased are shown.

[0353] <Container>

[0354] As a container for storing the drug solution, the following container was used.

[0355] EP-SUS: The liquid contact part is made of electrolytically polished stainless steel container

[0356] ·PFA: Containers with liquid contact parts coated with perfluoroalkoxyalkane

[0357] Table 1 shows the porosity of the chemical solution in each container.

[0358] <Purification Order>

[0359] One of the above-mentioned substances to be purified was selected and subjected to the distillation purification treatment described in Table 1.

[0360] In the column “Distillation Purification” in the table, “With-1” means that atmospheric distillation using a distillation column (theoretical plate number: 30 stages) was carried out twice, “With-2” means that atmospheric distillation using a distillation column (theoretical plate number: 30 stages) was carried out once, “With-3” means that atmospheric distillation using a distillation column (theoretical plate number: 25 stages) was carried out twice, “With-4” means that atmospheric distillation using a distillation column (theoretical plate number: 20 stages) was carried out twice, and “With-5” means that atmospheric distillation using a distillation column (theoretical plate number: 10 stages) was carried out once. "Yes-6" indicates that atmospheric distillation was carried out once using a distillation tower (theoretical plate number: 10 stages), "Yes-7" indicates that atmospheric distillation was carried out once using a distillation tower (theoretical plate number: 10 stages), "Yes-8" indicates that atmospheric distillation was carried out twice using a distillation tower (theoretical plate number: 8 stages), and "Yes-9" indicates that atmospheric distillation was carried out once using a distillation tower (theoretical plate number: 8 stages).

[0361] Next, the purified product after distillation was stored in a storage tank, and the purified product stored in the storage tank was filtered through filters 1 to 3 listed in Table 1 in order to be stored in the storage tank.

[0362] Next, as shown in Table 1 described later, in the examples where the "1st cycle" column is "Yes", the following circulation filtration treatment is performed: the purified material stored in the storage tank is filtered using the filters 4 to 5 described in Table 1, and the purified material after being filtered by the filter 5 is circulated on the upstream side of the filter 4, and filtered again using the filters 4 to 5. After the circulation filtration treatment, the drug solution is contained in a container.

[0363] As shown in Table 1 described later, in the Examples where the column "1st cycle" is "None", the above-mentioned circulation treatment was not performed, and the purified material stored in the storage tank was filtered using filters 4 to 6 described in Table 1.

[0364] Next, as shown in Table 1 described later, in the embodiment where the column "2nd cycle" is "Yes", the following circulation filtration treatment was performed: the obtained purified material was filtered using the filter 7 described in Table 1, and the purified material after being filtered by the filter 7 was circulated on the upstream side of the filter 7, and filtered again using the filter 7. After the circulation filtration treatment, the drug solution was contained in a container.

[0365] As shown in Table 1 described later, in the Examples where the column "2nd cycle" is "None", the above-mentioned circulation treatment was not performed, and the purified material was filtered using the filter 7 described in Table 1.

[0366] In addition, in the above-mentioned series of purification processes, the liquid contact parts of various devices (for example, distillation columns, pipes, storage tanks, etc.) that come into contact with the purified material are composed of electrolytically polished stainless steel.

[0367] The contents of organic components and metal components in the chemical solution were measured by the method shown below.

[0368] <Content of organic ingredients>

[0369] The content of organic components in the chemical solution was measured using a gas chromatograph-mass spectrometer (GC / MS) (manufactured by Agilent, GC: 7890B, MS: 5977B EI / CI MSD).

[0370] <Nitrate content>

[0371] The nitrate content in the chemical solution was measured using an ion chromatograph (for example, HIC-SP manufactured by Shimadzu Corporation).

[0372] <Content of Metal Components>

[0373] The content of metal components (metal ions and metal-containing particles) in the chemical solution was measured by a method using ICP-MS and SP-ICP-MS.

[0374] As for the apparatus, the following apparatus was used.

[0375] Manufacturer: PerkinElmer

[0376] Model: NexION350S

[0377] The following analysis software was used in the analysis.

[0378] Syngistix Nano Application Module for "SP-ICP-MS"

[0379] Syngistix for ICP-MS software

[0380] <Evaluation method>

[0381] (Deviation Evaluation)

[0382] First, an organic antireflection film-forming composition ARC29SR (manufactured by NISSAN CHEMICAL CORPORATION) was applied on a silicon substrate having a diameter of 300 mm and baked at 205° C. for 60 seconds to form an antireflection film having a thickness of 78 nm.

[0383] In order to improve coating properties, a pre-wetting liquid (manufactured by FUJIFILM Electronic Materials Co., Ltd., cyclohexanone) was dropped onto the surface of the silicon substrate on the anti-reflection film side on which the anti-reflection film was formed, and spin coating was performed.

[0384] Next, an actinic ray-sensitive or radiation-sensitive resin composition 1 described below was applied onto the antireflection film and pre-baked at 100° C. for 60 seconds to form a coating film with a film thickness of 150 nm.

[0385] Next, an ArF excimer laser scanner (NA 0.75) was used to irradiate the 2 ] The coating film was pattern exposed. Then, it was heated at 120°C for 60 seconds. Next, the solution of each example was used as a developer, stirred for 30 seconds and developed. Next, a negative resist pattern was formed by rotating the silicon substrate at 4000 rpm for 30 seconds. Then, the obtained negative resist pattern was post-baked at 200°C for 300 seconds. Through the above process, an L / S pattern with a line / space ratio of 1:1 was obtained. In addition, the line width was 65nm.

[0386] (Acticular ray-sensitive or radiation-sensitive resin composition 1)

[0387] Acid-decomposable resin (resin represented by the following formula (weight average molecular weight (Mw): 7500): the numerical value described in each repeating unit represents mol %): 100 parts by mass

[0388] [Chemical formula 10]

[0389]

[0390] The photoacid generator shown below: 8 parts by mass

[0391] [Chemical formula 11]

[0392]

[0393] The quencher shown below: 5 parts by mass (the mass ratio is 0.1:0.3:0.3:0.2 from the left). In the following quenchers, the weight average molecular weight (Mw) of the polymer type quencher is 5000. The numerical values ​​described in each repeating unit represent the molar ratio.

[0394] [Chemical formula 12]

[0395]

[0396] The hydrophobic resin shown below: 4 parts by mass (the mass ratio is set to 0.5:0.5 from the left). In addition, the weight average molecular weight (Mw) of the hydrophobic resin on the left side of the following hydrophobic resin is 7000, and the weight average molecular weight (Mw) of the hydrophobic resin on the right side is 8000. In addition, in each hydrophobic resin, the numerical value described in each repeating unit represents a molar ratio.

[0397] [Chemical formula 13]

[0398]

[0399] Solvent:

[0400] PGMEA (propylene glycol monomethyl ether acetate): 3 parts by mass

[0401] Cyclohexanone: 600 parts by mass

[0402] γ-BL (γ-butyrolactone): 100 parts by mass

[0403] The L / S pattern obtained above was observed and evaluated according to the following criteria. In addition, the deviation of the pattern spacing is a value (%) obtained by measuring the spacing between the patterns at 100 locations, calculating the calculated average of these, dividing the "difference" from the value farthest from the calculated average by the arithmetic mean, and multiplying by 100.

[0404] "AA": Deviation is less than 0.5%.

[0405] "A": The deviation is more than 0.5% and is 1.0% or less.

[0406] "B": The deviation exceeds 1.0% and is 1.2% or less.

[0407] "C": The deviation is more than 1.2% and is 1.5% or less.

[0408] "D": The deviation is more than 1.5% and is 2.0% or less.

[0409] "E": The deviation exceeds 2.0% and is 2.5% or less.

[0410] "F": The deviation is more than 2.5% and is 3.0% or less.

[0411] "G": Deviation exceeds 3.0%.

[0412] (Evaluation over time)

[0413] The chemical solution was stored at 30° C. for 1 year. Then, the above-mentioned (variation evaluation) was carried out using the stored chemical solution, and evaluation was performed according to the following criteria.

[0414] "A": The difference between the result of the variation evaluation using the drug solution before storage and the result of the variation evaluation using the drug solution after storage (the value of the variation evaluation using the drug solution after storage - the value of the variation evaluation using the drug solution before storage) is less than 3.0%

[0415] "B": The difference between the result of the variation evaluation using the drug solution before storage and the result of the variation evaluation using the drug solution after storage (the value of the variation evaluation using the drug solution after storage - the value of the variation evaluation using the drug solution before storage) is 3.0% or more and less than 5.0%

[0416] "C": The difference between the result of the variation evaluation using the drug solution before storage and the result of the variation evaluation using the drug solution after storage (the value of the variation evaluation using the drug solution after storage - the value of the variation evaluation using the drug solution before storage) is 5.0% or more

[0417] In Table 1, "Ratio 1 (isobutyl acetate / amyl acetates)" indicates the mass ratio of the content of isobutyl acetate to the content of amyl acetates.

[0418] “Ratio 2 (butyl propionate / amyl acetate)” indicates the mass ratio of the content of butyl propionate to the content of amyl acetate.

[0419] “Ratio 3 (dibutyl ether / amyl acetate)” represents the mass ratio of the content of dibutyl ether to the content of amyl acetate.

[0420] “Ratio 4 (sulfate / amyl acetate)” indicates the mass ratio of the content of sulfate to the content of amyl acetate.

[0421] “Ratio 5 (sulfate group / metal component)” indicates the mass ratio of the content of sulfate group to the content of metal component.

[0422] “Ratio 6 (isobutyl acetate / metal component)” indicates the mass ratio of the content of isobutyl acetate to the content of the metal component.

[0423] In Table 1, "<0.5" means less than 0.5. And, ">X" means more than X.

[0424] In Table 1, “E+number” means “10 数字 ”.

[0425] [Table 1]

[0426]

[0427] [Table 2]

[0428]

[0429] [Table 3]

[0430]

[0431] [Table 4]

[0432]

[0433] [Table 5]

[0434]

[0435] [Table 6]

[0436]

[0437] In Table 1, data of each Example and Comparative Example are shown in each row of Table 1 (Part 1) to (Part 6).

[0438] For example, in Example 1, as shown in Table 1 (No. 1), "PTFE 200 nm" was used as filter 1, as shown in Table 1 (No. 2), "PTFE 20 nm" was used as filter 4, as shown in Table 1 (No. 3), the content of isobutyl acetate in the drug solution was 2.0 mass ppm, as shown in Table 1 (No. 4), the content of 1-butanol in the drug solution was 30 mass ppm, as shown in Table 1 (No. 5), the ratio 1 (isobutyl acetate / amyl acetate) was 2.0, as shown in Table 1 (No. 6), the deviation evaluation was "C". The same is true for other Examples and Comparative Examples.

[0439] As shown in Table 1, it was confirmed that when the drug solution of the present invention was used, the desired effect was obtained.

[0440] Among them, from the comparison between Example 4 and Example 12 and other examples, it was confirmed that when the porosity was 5 to 30 volume %, the time evaluation was more excellent.

[0441] Furthermore, as shown in Example 5 and Example 18, it was confirmed that when any one of the following requirements 1 to 12 is satisfied, the effect is more excellent.

[0442] Furthermore, as shown in other embodiments, when any one of the necessary conditions 1 to 12 is not satisfied, (the deviation evaluation) becomes "A", when any two of the necessary conditions 1 to 12 are not satisfied, (the deviation evaluation) becomes "B", when any three of the necessary conditions 1 to 12 are not satisfied, (the deviation evaluation) becomes "C", when any four of the necessary conditions 1 to 12 are not satisfied, (the deviation evaluation) becomes "D", when any five of the necessary conditions 1 to 12 are not satisfied, (the deviation evaluation) becomes "E", and when any six to eight of the necessary conditions 1 to 12 are not satisfied, (the deviation evaluation) becomes "F".

[0443] Requirement 1: The content of amyl acetate is 1.0 to 300 ppm by mass relative to the total mass of the drug solution

[0444] Requirement 2: The content of butyl propionate is 1.0 to 700 ppm by mass relative to the total mass of the drug solution

[0445] Requirement 3: The content of butyl formate is 1.0 to 50 ppm by mass relative to the total mass of the drug solution

[0446] Requirement 4: The content of dibutyl ether is 5.0 to 500 ppm by mass relative to the total mass of the drug solution

[0447] Requirement 5: The sulfate content is 1.0 to 200 ppm by mass relative to the total mass of the drug solution

[0448] Necessary condition 6: The metal content is 0.01 to 150 ppt relative to the total mass of the liquid medicine.

[0449] Necessary condition 7: The mass ratio of the content of isobutyl acetate to the content of amyl acetate is 0.5 to 300.

[0450] Necessary condition 8: The mass ratio of the content of butyl propionate to the content of amyl acetate (ratio 2) is 0.10 to 10.0

[0451] Requirement 9: The mass ratio of the content of dibutyl ether to the content of amyl acetate (ratio 3) is greater than 0.5 and is 35.0 or less

[0452] Requirement 10: The mass ratio of the content of sulfate to the content of amyl acetate (ratio 4) is 0.01 to 10.0

[0453] Necessary condition 11: The mass ratio of the content of sulfate to the content of metal components (ratio 5) is 10 4 ~10 8

[0454] Necessary condition 12: The mass ratio of the content of isobutyl acetate to the content of the metal component (ratio 6) is 10 4 ~10 7

[0455] Furthermore, the present inventors have studied the characteristics of the drug solution of Patent Document 1 and have found that the drug solution described in Patent Document 1 does not provide the expected effects.

[0456] <Example 26>

[0457] In the method of Example 6, after development, the chemical solution of Example 6 was used as a rinse liquid, and the formed resist pattern was cleaned, and then post-baking was performed. As a result of the evaluation performed in the same order as the above (deviation evaluation), the deviation evaluation was "AA". Based on this result, it was confirmed that the effect was further improved by implementing the process of using the chemical solution of the present invention as a rinse liquid.

[0458] <Example 27>

[0459] In the method of Example 6, after development, a mixed solution of the chemical solution of Example 6 (97% by mass) and 4-methyl-2-pentanol (3% by mass) was used as a rinse solution to clean the formed resist pattern, and then post-baking was performed. As a result of evaluation in the same order as the above (deviation evaluation), the deviation evaluation was "AA". Based on this result, it was confirmed that the effect is further improved by implementing a process in which the chemical solution of the present invention is used as a rinse solution.

[0460] <Example 28 to Example 32>

[0461] Various evaluations were performed according to the same procedures as in Examples 21 to 25, except that (actinic ray or radiation-sensitive resin composition 2) described later was used instead of (actinic ray or radiation-sensitive resin composition 1).

[0462] In Examples 28 to 32, (Deviation Evaluation) and (Evaluation over Time) were "AA" and "A", respectively, similar to Examples 21 to 25. From these results, it was confirmed that the same effect can be obtained even when the actinic ray-sensitivity or radiation-sensitive resin composition is changed.

[0463] (Acticular ray-sensitive or radiation-sensitive resin composition 2)

[0464] Acid-decomposable resin (resin represented by the following formula (weight average molecular weight (Mw): 8000): the numerical value described in each repeating unit represents mol %): 100 parts by mass

[0465] [Chemical formula 14]

[0466]

[0467] The photoacid generator shown below: 12 parts by mass (the mass ratio is 0.5:0.5 from the left.)

[0468] [Chemical formula 15]

[0469]

[0470] The following quencher: 5 parts by mass (the mass ratio is 0.3:0.7 from the left.)

[0471] [Chemical formula 16]

[0472]

[0473] The hydrophobic resin shown below: 5 parts by mass (the mass ratio is set to 0.8:0.2 from the top). In addition, the weight average molecular weight (Mw) of the hydrophobic resin in the upper section of the following hydrophobic resin is 8000, and the weight average molecular weight (Mw) of the hydrophobic resin in the lower section is 6000. In addition, in each hydrophobic resin, the numerical value described in each repeating unit represents a molar ratio.

[0474] [Chemical formula 17]

[0475]

[0476] [Chemical formula 18]

[0477]

[0478] Solvent:

[0479] PGMEA (propylene glycol monomethyl ether acetate): 3 parts by mass

[0480] Cyclohexanone: 600 parts by mass

[0481] γ-BL (γ-butyrolactone): 100 parts by mass

[0482] <Example 33 to Example 37>

[0483] Various evaluations were performed according to the same procedures as in Examples 21 to 25, except that (actinic ray or radiation-sensitive resin composition 3) described later was used instead of (actinic ray or radiation-sensitive resin composition 1).

[0484] In Examples 33 to 37, (Deviation Evaluation) and (Evaluation over Time) were "AA" and "A", respectively, similar to Examples 21 to 25. From these results, it was confirmed that the same effect can be obtained even when the actinic ray-sensitivity or radiation-sensitive resin composition is changed.

[0485] (Acticular ray-sensitive or radiation-sensitive resin composition 3)

[0486] Acid-decomposable resin (resin represented by the following formula (weight average molecular weight (Mw): 8000): the numerical value described in each repeating unit represents mol %): 100 parts by mass

[0487] [Chemical formula 19]

[0488]

[0489] The photoacid generator shown below: 15 parts by mass

[0490] [Chemical formula 20]

[0491]

[0492] The following quencher: 7 parts by mass (the mass ratio is 1:1 from left to right.)

[0493] [Chemical formula 21]

[0494]

[0495] The hydrophobic resin shown below: 20 parts by mass (the mass ratio is 3:7 from the top). In addition, the weight average molecular weight (Mw) of the hydrophobic resin in the upper section of the following hydrophobic resin is 10,000, and the weight average molecular weight (Mw) of the hydrophobic resin in the lower section is 7,000. In addition, in the hydrophobic resin shown in the lower section, the molar ratios of the repeating units are 0.67 and 0.33 from the left.

[0496] [Chemical formula 22]

[0497]

[0498] [Chemical formula 23]

[0499]

[0500] Solvent:

[0501] PGMEA (propylene glycol monomethyl ether acetate): 50 parts by mass

[0502] PGME (propylene glycol monomethyl ether): 100 parts by mass

[0503] 2-Heptanone: 100 parts by mass

[0504] γ-BL (γ-butyrolactone): 500 parts by mass

[0505] <Example 38 to Example 42>

[0506] Various evaluations were carried out according to the same procedures as in Examples 21 to 25, except that (actinic ray or radiation-sensitive resin composition 4) described later was used instead of (actinic ray or radiation-sensitive resin composition 1).

[0507] In Examples 38 to 42, (Deviation Evaluation) and (Evaluation over Time) were "AA" and "A", respectively, similar to Examples 21 to 25. From these results, it was confirmed that the same effect can be obtained even when the actinic ray-sensitivity or radiation-sensitive resin composition is changed.

[0508] (Acticular ray-sensitive or radiation-sensitive resin composition 4)

[0509] Acid-decomposable resin (resin represented by the following formula (weight average molecular weight (Mw): 6500): the numerical value described in each repeating unit represents mol %): 80 parts by mass

[0510] [Chemical formula 24]

[0511]

[0512] The photoacid generator shown below: 15 parts by mass

[0513] [Chemical formula 25]

[0514]

[0515] The following quencher: 5 parts by mass

[0516] [Chemical formula 26]

[0517]

[0518] The following hydrophobic resin (weight average molecular weight (Mw) is 5000): 60 parts by mass

[0519] [Chemical formula 27]

[0520]

[0521] Solvent:

[0522] PGMEA (propylene glycol monomethyl ether acetate): 70 parts by mass

[0523] HBM (methyl 2-hydroxybutyrate): 100 parts by mass

[0524] Cyclohexanone: 700 parts by mass

[0525] <Example 43 to Example 47>

[0526] Various evaluations were carried out according to the same procedures as in Examples 21 to 25, except that (actinic ray or radiation-sensitive resin composition 5) described later was used instead of (actinic ray or radiation-sensitive resin composition 1).

[0527] In addition, the acid-decomposable resin used in (actinic ray or radiation-sensitive resin composition 5) is not suitable for a resin containing 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).

[0528] In Examples 43 to 47, the results obtained were worse than those of (variation evaluation) of Examples 21 to 25. More specifically, (variation evaluation) of Examples 43 to 47 was A.

[0529] (Acticular ray-sensitive or radiation-sensitive resin composition 5)

[0530] Acid-decomposable resin (resin represented by the following formula (weight average molecular weight (Mw): 6500): the content of each repeating unit is 20 mol% and 80 mol% from the left): 0.78 g

[0531] [Chemical formula 28]

[0532]

[0533] Photoacid generator as shown below: 0.19 g

[0534] [Chemical formula 29]

[0535]

[0536] Quencher as shown below: 0.03 g

[0537] [Chemical formula 30]

[0538]

[0539] Solvent:

[0540] Propylene glycol monomethyl ether acetate: 67.5g

[0541] Ethyl lactate: 7.5g

Claims

1. A liquid medicine comprising n-butyl acetate and isobutyl acetate, wherein: The content of n-butyl acetate is 99.000 mass % to 99.999 mass % relative to the total mass of the liquid medicine. The content of the isobutyl acetate is 1.0 ppm by mass to 1000 ppm by mass relative to the total mass of the chemical solution.

2. The liquid medicine according to claim 1, further comprising amyl acetate, The content of the amyl acetate is 1.0 ppm by mass to 300 ppm by mass relative to the total mass of the chemical solution.

3. The liquid medicine according to claim 2, wherein: The amyl acetates include a compound selected from the group consisting of 1-methylbutyl acetate, 2-methylbutyl acetate, and 3-methylbutyl acetate.

4. The liquid medicine according to claim 2, wherein: The mass ratio of the isobutyl acetate content to the amyl acetate content is 0.5-300.

5. The liquid medicine according to claim 1, further comprising butyl propionate, The content of the butyl propionate is 1.0 ppm by mass to 700 ppm by mass relative to the total mass of the chemical solution.

6. The liquid medicine according to claim 5, further comprising amyl acetate, The mass ratio of the butyl propionate content to the amyl acetate content is 0.10 to 10.

0.

7. The liquid medicine according to claim 1 or 2, further comprising butyl formate, The content of the butyl formate is 1.0 ppm by mass to 50 ppm by mass relative to the total mass of the chemical solution.

8. The liquid medicine according to claim 1, further comprising dibutyl ether, The content of the dibutyl ether is 5.0 ppm by mass to 500 ppm by mass relative to the total mass of the chemical solution.

9. The liquid medicine according to claim 8, further comprising amyl acetate, The mass ratio of the content of the dibutyl ether to the content of the amyl acetates is more than 0.5 and is 35.0 or less.

10. The liquid medicine according to claim 1 or 2, further comprising 1-butanol, The content of the 1-butanol is 5.0 ppm by mass to 3500 ppm by mass relative to the total mass of the chemical solution.

11. The liquid medicine according to claim 1, further comprising sulfate, The content of the sulfate radical is 1.0 ppm by mass to 200 ppm by mass relative to the total mass of the chemical solution.

12. The drug solution according to claim 11, further comprising amyl acetate, The mass ratio of the sulfate content to the amyl acetate content is 0.01 to 10.

0.

13. The liquid medicine according to claim 1, further comprising a metal component, The content of the metal component is 0.01 to 150 ppt by mass relative to the total mass of the chemical solution.

14. The liquid medicine according to claim 13, wherein: The mass ratio of the content of isobutyl acetate to the content of the metal component is 10 4 ~10 7 .

15. The liquid medicine according to claim 1 or 2, further comprising sulfate and a metal component. The mass ratio of the sulfate content to the metal content is 10 4 ~10 8 .

16. The chemical solution according to claim 1 or 2, which is used as a developer or rinser. 17 . A drug solution container comprising a container and the drug solution according to claim 1 contained in the container.

18. The drug solution container according to claim 17, wherein: The liquid contact portion that contacts the chemical solution in the container is formed of electropolished stainless steel or fluorine-based resin.

19. The drug solution container according to claim 17 or 18, wherein: The porosity in the container obtained by formula (1) is 5% to 30% by volume. Formula (1): Porosity={1-(volume of the drug solution in the container / container volume of the container)}×100.

20. A method for forming a resist pattern, comprising: A step of forming a coating film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition; A step of exposing the coating film to light; and a step of developing the exposed coating film using a developer to form a resist pattern, In the resist pattern forming method, the developer is the chemical solution according to any one of claims 1 to 16.

21. A method for forming a resist pattern, comprising: A step of forming a coating film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition; A step of exposing the coating film to light; A step of developing the exposed coating film using a developer to form a resist pattern; and a step of cleaning the resist pattern using a rinse solution, In the resist pattern forming method, the rinse liquid is the chemical solution according to any one of claims 1 to 16.

22. A method for manufacturing a semiconductor chip, comprising the resist pattern forming method according to claim 20 or 21.

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