Processing liquid for semiconductor manufacturing, method for manufacturing same, pattern forming method, and method for manufacturing electronic device

Abstract

The purpose of the present invention is to provide a processing liquid for semiconductor production, said processing liquid being capable of suppressing deterioration of lithography performance or generation of defects, and being capable of producing a fine resist pattern or a fine semiconductor element. A processing liquid for semiconductor manufacturing according to an embodiment of the present invention contains a compound (A) satisfying requirement (a), one or more compounds (B) satisfying requirement (b), and one or more inorganic substances (C) containing any element selected from Al, B, S, N, and K. Here, the total content of the compound (B) is 10 <-10 >-0.1 mass%, and the ratio (P) of the compound (B) represented by formula I to the inorganic substance (C) is 10 < 3 >-10 <-6 >.

Description

[0001] This application is a divisional application of the application No. 201780020677.3 filed by the applicant and entitled “Processing liquid for semiconductor manufacturing, manufacturing method thereof, pattern forming method and manufacturing method of electronic device”. The filing date of the parent case is March 16, 2017, and the priority date is March 31, 2016. Technical Field

[0002] The present invention relates to a semiconductor manufacturing processing liquid such as a developer, a rinser, a pre-wet liquid, a stripper, etc., used in the manufacturing process of a semiconductor device, a manufacturing method thereof, a pattern forming method, and a manufacturing method of an electronic device. Background Art

[0003] The manufacturing process of semiconductor devices includes various processes such as photolithography, etching, ion implantation, and stripping. Here, after each process is completed or before the next process is transferred, a process of treating unnecessary organic and inorganic substances with a treatment liquid is usually included. For example, it includes a developing process of treating the resist film after exposure with a developer, a stripping process of treating the resist remaining on the surface of the substrate after substrate processing with a stripping liquid, and a rinsing process of further purifying the surface with a rinsing liquid after the stripping process or the developing process.

[0004] The various processing liquids (hereinafter referred to as "semiconductor manufacturing processing liquids") used in the manufacturing process of such semiconductor devices are required to be of high purity, such as developer, rinser, pre-wet liquid, stripper, etc. With the progress of miniaturization and high functionality of semiconductors, the overall market demand for high-purity processing liquids has also increased, and the market is expected to expand in the future.

[0005] The so-called high-purity treatment liquid for semiconductor manufacturing refers to low metal concentration and low particle concentration as basic conditions. For example, Japanese Patent Publication No. 2015-84122 discloses a technology that can reduce the generation of particles in organic developer. In addition, the metal in the treatment liquid causes a phenomenon called migration in which the metal diffuses into the object material during processing. Migration hinders the transmission of electrical signals and becomes the cause of adverse conditions such as short circuits. In addition, not only that, the metal itself may become garbage remaining in the form of residue after processing as a core, which becomes the cause of deterioration of lithography performance or defects, and has an adverse effect on the formation of fine resist patterns or semiconductor elements. Based on this background, there is a strong demand for further high-purity treatment liquid for semiconductor manufacturing. Summary of the invention

[0006] Technical issues to be solved by the invention

[0007] The semiconductor processing liquid used in the current semiconductor manufacturing industry has reached a fairly high purity. For example, the total metal concentration of the rinsing liquid using isopropanol (IPA) of FEUS, which emphasizes high purity and low metal, is tens to hundreds of mass ppt (parts per trillion). However, the performance required in the future, such as a metal concentration of less than 10 mass ppt, cannot be met with the current performance.

[0008] The present invention was developed under such background, and its subject is to provide a semiconductor manufacturing process liquid that can suppress the deterioration of lithography performance or the generation of defects and can manufacture a fine resist pattern or a fine semiconductor element, and also to provide a method for manufacturing the semiconductor manufacturing process liquid. In addition, the present invention is to provide a pattern forming method using the semiconductor manufacturing process liquid, and a method for manufacturing a semiconductor element including the pattern forming method.

[0009] Means for solving technical problems

[0010] The present invention is described below in one aspect. [1]

[0012] A processing liquid for semiconductor manufacturing, comprising:

[0013] A compound (A) satisfying the following requirement (a);

[0014] One or more compounds (B) satisfying the following requirement (b); and

[0015] One or more inorganic substances (C) containing any element selected from Al, B, S, N and K,

[0016] The total content of compound (B) in the above treatment solution is 10 -10 ~0.1% by mass

[0017] The ratio P of the compound (B) represented by the following formula I to the inorganic substance (C) is 10 3 ~10 -6 .

[0018] Requirement (a): A compound selected from alcohol compounds, ketone compounds and ester compounds, the content of which in the treatment liquid is 90.0 to 99.9999999% by mass.

[0019] Requirement (b): A compound having 6 or more carbon atoms selected from alcohol compounds, ketone compounds, ester compounds, ether compounds and aldehyde compounds, and containing 10 -11 ~0.1 mass % of the compound.

[0020] P = [total mass of inorganic substance (C)] / [total mass of compound (B)] Formula I [2]

[0022] The semiconductor manufacturing processing liquid according to [1], wherein the inorganic substance (C) is a compound containing any element selected from the group consisting of Al, B and S. [3]

[0024] The semiconductor manufacturing process liquid according to [1] or [2], wherein the content of each of the one or two or more inorganic substances (C) contained in the semiconductor manufacturing process liquid is 0.0001 to 100 ppb by mass. [4]

[0026] The semiconductor manufacturing process liquid according to any one of [1] to [3], wherein the content of each of the one or two or more inorganic substances (C) contained in the semiconductor manufacturing process liquid is 0.001 to 100 ppb by mass. [5]

[0028] The semiconductor manufacturing processing liquid according to any one of [1] to [4], comprising Na, Ca and Fe, wherein the content of each atom is 0.01 mass ppt to 1000 mass ppb. [6]

[0030] The semiconductor manufacturing processing liquid according to any one of [1] to [5], wherein the total content of the metal particles measured by SNP-ICP-MS method is 0.001 to 100 ppt by mass. [7]

[0032] The semiconductor manufacturing processing liquid according to any one of [1] to [6], wherein the total content of the metal particles measured by SNP-ICP-MS method is 1 to 100 ppt by mass. [8]

[0034] The semiconductor manufacturing processing liquid according to any one of [1] to [7], comprising at least one compound represented by the following formulas I to V as compound (B).

[0035] [Chemical formula 1]

[0036]

[0037] In Formula I, R1 and R2 each independently represent an alkyl group or a cycloalkyl group, or are bonded to each other to form a ring.

[0038] In Formula II, R3 and R4 are independently hydrogen atoms, alkyl groups, alkenyl groups, cycloalkyl groups or cycloalkenyl groups, or are bonded to each other to form a ring. R3 and R4 are not hydrogen atoms at the same time.

[0039] In formula III, R5 represents an alkyl group or a cycloalkyl group.

[0040] In Formula IV, R6 and R7 each independently represent an alkyl group or a cycloalkyl group, or are bonded to each other to form a ring.

[0041] In Formula V, R8 and R9 each independently represent an alkyl group, a cycloalkyl group, or are bonded to each other to form a ring; and L represents a single bond or an alkylene group. [9]

[0043] The semiconductor manufacturing processing liquid according to any one of [1] to [8], wherein the ratio Q of the compound (A) represented by the following formula II to the compound (B) is 10 4 ~10 10 .

[0044] Q = [total mass of compound (A)] / [total mass of compound (B)] Formula II

[10]

[0046] A semiconductor manufacturing process liquid comprising two or more semiconductor manufacturing process liquids according to any one of [1] to [9].

[11]

[0048] The semiconductor manufacturing processing liquid according to any one of [1] to

[10] , wherein the semiconductor manufacturing processing liquid is a developer.

[12]

[0050] The semiconductor manufacturing processing liquid according to any one of [1] to

[10] , wherein the semiconductor manufacturing processing liquid is a rinse liquid.

[13]

[0052] The semiconductor manufacturing processing liquid according to any one of [1] to

[10] , wherein the semiconductor manufacturing processing liquid is a pre-wetting liquid.

[14]

[0054] A method for producing a semiconductor manufacturing process liquid, which is a method for producing a semiconductor manufacturing process liquid according to any one of [1] to

[13] , the method for producing a semiconductor manufacturing process liquid comprising:

[0055] allowing one or more raw materials to react in the presence of a catalyst to synthesize compound (A) and obtain a crude liquid containing compound (A), compound (B) and inorganic substance (C); and

[0056] The above crude liquid is purified.

[15]

[0058] A pattern forming method, comprising:

[0059] A step of coating an actinic ray-sensitive or radiation-sensitive resin composition on a substrate to form an actinic ray-sensitive or radiation-sensitive film;

[0060] A step of exposing the above-mentioned photosensitive ray or radiation-sensitive film to light; and

[0061] A step of treating the substrate or the actinic ray-sensitive or radiation-sensitive film using the semiconductor manufacturing processing liquid according to any one of claims 1 to 13.

[16]

[0063] The pattern forming method according to

[15] , wherein the process of using the semiconductor manufacturing processing liquid to process the substrate or the photosensitive ray or radiation-sensitive film at least includes the process of using the semiconductor manufacturing processing liquid as a developer to develop the photosensitive ray or radiation-sensitive film.

[17]

[0065] A pattern forming method according to

[15] or

[16] , wherein the process of using the semiconductor manufacturing processing liquid to process the substrate or the photosensitive ray or radiation-sensitive film at least includes a process of using the semiconductor manufacturing processing liquid as a rinse liquid to clean the photosensitive ray or radiation-sensitive film.

[18]

[0067] A pattern forming method according to any one of

[15] to

[17] , wherein the process of using the above-mentioned semiconductor manufacturing processing liquid to treat the above-mentioned substrate or the above-mentioned photosensitive ray or radiation-sensitive film at least includes a process of using the above-mentioned semiconductor manufacturing processing liquid as a pre-wetting liquid to treat the above-mentioned substrate.

[19]

[0069] A pattern forming method according to any one of

[15] to

[18] , wherein a semiconductor manufacturing processing liquid having a dissolution rate of 0.0016 to 0.33 nm / sec at 23° C. when the actinic ray-sensitive or radiation-sensitive film before exposure is immersed is used as the semiconductor manufacturing processing liquid.

[0070]

[20] A method for manufacturing an electronic device, comprising the pattern forming method according to any one of

[15] to

[19] .

[0071] Effects of the Invention

[0072] The present invention can provide a semiconductor manufacturing process liquid that can suppress the deterioration of photolithography performance or the generation of defects and can manufacture a fine resist pattern or a fine semiconductor element, and can also provide a method for manufacturing the semiconductor manufacturing process liquid. In addition, the present invention can provide a pattern forming method using the semiconductor manufacturing process liquid, and a method for manufacturing a semiconductor element including the pattern forming method. BRIEF DESCRIPTION OF THE DRAWINGS

[0073] Figure 1 This is a schematic diagram showing one form of a production apparatus that can be used in the method for producing a processing liquid according to the embodiment of the present invention.

[0074] Figure 2 It is a schematic diagram showing another form of a production apparatus that can be used in the production method of the processing liquid according to the embodiment of the present invention. DETAILED DESCRIPTION

[0075] In the notation of a group (atomic group) in this specification, a notation not describing substitution and unsubstitution includes not only a group (atomic group) without a substituent but also a group (atomic group) with a substituent. For example, the so-called "alkyl" includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group with a substituent (substituted alkyl group).

[0076] In addition, the "actinic ray" or "radiation" in this specification refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet (EUV) rays, X-rays, or electron beams (EB). In addition, in the present invention, the so-called "light" refers to actinic rays or radiation.

[0077] In addition, unless otherwise specified, the term "exposure" in this specification refers not only to exposure using a mercury lamp, extreme ultraviolet light represented by an excimer laser, X-rays, EUV light, etc., but also includes drawing using a particle beam such as an electron beam and an ion beam.

[0078] In this specification, "(meth)acrylate" means "at least one of acrylate and methacrylate". In addition, "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid". In addition, in this specification, the numerical range expressed by "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0079] Hereinafter, embodiments of the present invention will be described in detail.

[0080] <Processing liquid for semiconductor manufacturing>

[0081] In the present invention, the "processing liquid for semiconductor manufacturing" is, as described above, a processing liquid used to treat organic matter in the manufacturing process of semiconductor devices including a photolithography process, an etching process, an ion implantation process, a stripping process, etc., after the completion of each process or before transferring to the next process, and specifically, it is a processing liquid used as a developer, a rinse liquid, a pre-wetting liquid, a stripping liquid, etc.

[0082] The processing liquid for semiconductor manufacturing of the present invention (hereinafter also referred to as "the processing liquid of the present invention", etc.) comprises: a compound (A) that satisfies the following requirement (a); at least one compound (B) that satisfies the following requirement (b); and at least one inorganic substance (C) having any element selected from Al, B, S, N and K.

[0083] Requirement (a): A compound selected from alcohol compounds, ketone compounds and ester compounds, the content of which in the treatment liquid of the present invention is 90.0 to 99.9999999% by mass.

[0084] Requirement (b): A compound having 6 or more carbon atoms selected from alcohol compounds, ketone compounds, ester compounds, ether compounds and aldehyde compounds, and a content of 10 in the treatment liquid of the present invention -11 ~0.1 mass % of the compound.

[0085] The compound (A) is a main component contained in the treatment liquid of the present invention at a content of 90.0 to 99.9999999 mass %, and the content is preferably, for example, 99.999 to 99.9999999 mass %, and particularly preferably 99.9999 to 99.9999999 mass %.

[0086] The treatment liquid of the present invention may be a combination of compound (A) and other compounds. In this case, the content of the other compound is, for example, preferably 0.01 to 5.00% by mass, more preferably 0.1 to 2.00% by mass.

[0087] In this case, examples of the other compound include dimethyl sulfoxide and the like.

[0088] In the treatment liquid of the present invention, compound (B) is a compound contained as an impurity, and the total content of the compound (B) is 10% relative to the total mass of the treatment liquid. -10 Here, the total content of the compound (B) is the content described in the requirement (b), that is, the content is between 10 -11When there is one compound (B) in the treatment liquid with a content of 0.1% to 0.1% by mass, it refers to the content of the one compound (B). In addition, when there are two or more compounds (B) satisfying the content requirement described in requirement (b), it refers to the total content of the two or more compounds (B).

[0089] The content of the compound (B) described in the requirement (b) is preferably 10 -10 ~10 -4 Mass %, more preferably 10 -10 ~10 -5 quality%.

[0090] In the treatment liquid of the present invention, the inorganic substance (C) containing any element selected from Al, B, S, N and K is an inorganic substance mixed in during the synthesis of the treatment liquid of the present invention and is mainly derived from the catalyst.

[0091] In one embodiment, the treatment liquid of the present invention contains a compound containing any element selected from the group consisting of Al, B and S as the inorganic substance (C).

[0092] In the purification step of the treatment liquid, most of the compound (B) and the inorganic substance (C) are removed, but a small amount remains in the purified treatment liquid.

[0093] The present invention is developed based on the knowledge that the ratio of the compound (B) to the inorganic substance (C) contained in the processing liquid for semiconductor manufacturing has a significant influence on the lithography performance or defect performance, and one of the characteristics of the present invention is that the P value represented by the following formula I, which is the ratio of the inorganic substance (C) to the compound (B), is 10 3 ~10 -6 range.

[0094] P = [total mass of inorganic substances (C)] / [total mass of compound (B)] Formula I

[0095] When the ratio P of the inorganic substance (C) to the compound (B) is 10 3 ~10 -6 In the case of the range of , the deterioration of the lithography performance or the generation of defects can be suppressed, and a fine resist pattern or a fine semiconductor element can be provided. Although the mechanism of this phenomenon is not necessarily clear, it is speculated that if the balance between the compound (B) and the inorganic substance (C) contained in the processing liquid collapses, for example, when the processing is performed using each processing liquid such as a developer, a rinse liquid, a pre-wet liquid, and a stripping liquid, it will cause a specific development that causes the deterioration of the lithography performance or the generation of defects.

[0096] The P value represented by Formula I, which is the ratio of the inorganic substance (C) to the compound (B), is preferably 10 3 ~10 -5, more preferably 10 2 ~10 -4 .

[0097] As described above, the compound (B) is present in an amount of 10% by weight relative to the total weight of the treatment liquid. -10 The impurities contained in trace amounts in the range of 0.1% to 0.1% by mass are preferably present in the ratio Q of the compound (A) to the compound (B) represented by the following formula II to be 10 from the viewpoint of improving the photolithographic performance and suppressing defects. 4 ~10 10 .

[0098] Q = [total mass of compound (A)] / [total mass of compound (B)] Formula II

[0099] Although the mechanism of this phenomenon is not clear, it is confirmed that the effect of the present invention is further improved when the ratio Q of the compound (A) to the compound (B) is within the above range.

[0100] The Q value represented by Formula II, which is the ratio of compound (A) to compound (B), is more preferably 10 5 ~10 10 , more preferably 10 6 ~10 10 .

[0101] In the treatment liquid of the present invention, the content of the inorganic substance (C) is preferably 0.0001 to 100 mass ppb (parts per billion), more preferably 0.001 to 100 mass ppb, based on the total mass of the treatment liquid. In the case where the treatment liquid of the present invention contains two or more inorganic substances (C), the content of each inorganic substance (C) is preferably 0.0001 to 100 mass ppb, more preferably 0.001 to 100 mass ppb.

[0102] When the concentration of each inorganic substance (C) is 100 mass ppb or less, it is possible to suppress the situation where these compounds remain on the substrate as nuclei of residual components during processing and become the cause of defects.

[0103] On the other hand, it is generally believed that the less the inorganic substance (C), the better, but in the case of less than 0.001 mass ppb, it is confirmed that the defects tend to increase again. Although the mechanism may not be clear, it is inferred that when the inorganic substance (C) is removed from the substrate, it is removed in the form of being involved in the compound (B) and in the form of a block of ions or compounds to a certain extent. Therefore, it is believed that when the inorganic substance (C) is too little, the removal rate of the inorganic substance (C) and the compound (B) deteriorates, and the remaining on the substrate becomes the cause of the defect.

[0104] As described above, the compound (A) contained in the treatment liquid of the present invention is a compound selected from alcohol compounds, ketone compounds and ester compounds, and the treatment liquid of the present invention contains one or more of these compounds.

[0105] Examples of the alcohol compound include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, cyclopentanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl- Alcohols (monohydric alcohols) such as 2-pentanol, 4-methyl-3-pentanol, cyclohexanol, and 3-methoxy-1-butanol, or glycol solvents such as ethylene glycol, diethylene glycol, and triethylene glycol, or glycol ether solvents containing hydroxyl groups such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol), diethylene glycol monomethyl ether, methoxymethyl butanol, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether.

[0106] Examples of the ketone compound include acetone, 1-hexanone, 2-hexanone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, acetyl carbinol, propylene carbonate, γ-butyrolactone, etc. The ketone compound as the compound (A) also includes a diketone compound.

[0107] Examples of the ester compound include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isopropyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, and isopropyl propionate.

[0108] In one embodiment, compound (A) may be a mixture of compounds having the same number of carbon atoms but different structures, such as isomers. The compounds having the same number of carbon atoms but different structures may be contained in only one type, or in plural types as described above.

[0109] In one embodiment, the compound (A) preferably has a flash point of 80° C. or lower, more preferably 75° C. or lower, and even more preferably 65° C. or lower. The lower limit of the flash point is not particularly limited, but is preferably 23° C. or higher, for example.

[0110] The compound (B) contained in the treatment liquid of the present invention is a compound having 6 or more carbon atoms selected from alcohol compounds, ketone compounds, ester compounds, ether compounds and aldehyde compounds as described above, and the treatment liquid of the present invention contains one or more of these compounds. The number of carbon atoms of the compound (B) is preferably 6 to 12, more preferably 6 to 10.

[0111] In one embodiment of the present invention, the compound (B) is preferably at least one compound represented by the following formulas I to V.

[0112] [Chemical formula 2]

[0113]

[0114] In Formula I, R1 and R2 each independently represent an alkyl group or a cycloalkyl group, or are bonded to each other to form a ring.

[0115] The alkyl group and cycloalkyl group represented by R1 and R2 are preferably an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 6 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 6 to 8 carbon atoms.

[0116] The ring formed by bonding R1 and R2 to each other is a lactone ring, more preferably a lactone ring having 4 to 9 members, and even more preferably a lactone ring having 4 to 6 members.

[0117] Furthermore, R1 and R2 satisfy the relationship that the number of carbon atoms in the compound represented by Formula I is 6 or more.

[0118] In Formula II, R3 and R4 are independently hydrogen atoms, alkyl groups, alkenyl groups, cycloalkyl groups or cycloalkenyl groups, or are bonded to each other to form a ring. R3 and R4 are not necessarily hydrogen atoms.

[0119] As the alkyl group represented by R3 and R4, for example, an alkyl group having 1 to 12 carbon atoms is preferred, and an alkyl group having 1 to 8 carbon atoms is more preferred.

[0120] As the alkenyl group represented by R3 and R4, for example, an alkenyl group having 2 to 12 carbon atoms is preferred, and an alkenyl group having 2 to 8 carbon atoms is more preferred.

[0121] The cycloalkyl group represented by R3 and R4 is preferably a cycloalkyl group having 6 to 12 carbon atoms, and more preferably a cycloalkyl group having 6 to 8 carbon atoms.

[0122] As the cycloalkenyl group represented by R3 and R4, for example, a cycloalkenyl group having 3 to 12 carbon atoms is preferred, and a cycloalkenyl group having 6 to 8 carbon atoms is more preferred.

[0123] The ring formed by R3 and R4 bonding to each other is a cyclic ketone structure, which may be a saturated cyclic ketone or an unsaturated cyclic ketone. The cyclic ketone is preferably a 6- to 10-membered ring, more preferably a 6- to 8-membered ring.

[0124] Furthermore, R3 and R4 satisfy the relationship that the number of carbon atoms of the compound represented by Formula II is 6 or more.

[0125] In formula III, R5 represents an alkyl group or a cycloalkyl group.

[0126] The alkyl group represented by R5 is an alkyl group having 6 or more carbon atoms, preferably an alkyl group having 6 to 12 carbon atoms, and more preferably an alkyl group having 6 to 10 carbon atoms.

[0127] The alkyl group may have an ether bond in the chain, and may have a substituent such as a hydroxyl group.

[0128] The cycloalkyl group represented by R5 is a cycloalkyl group having 6 or more carbon atoms, preferably a cycloalkyl group having 6 to 12 carbon atoms, and more preferably a cycloalkyl group having 6 to 10 carbon atoms.

[0129] In Formula IV, R6 and R7 each independently represent an alkyl group or a cycloalkyl group, or are bonded to each other to form a ring.

[0130] As the alkyl group represented by R6 and R7, for example, an alkyl group having 1 to 12 carbon atoms is preferred, and an alkyl group having 1 to 8 carbon atoms is more preferred.

[0131] The cycloalkyl group represented by R6 and R7 is preferably a cycloalkyl group having 6 to 12 carbon atoms, and more preferably a cycloalkyl group having 6 to 8 carbon atoms.

[0132] The ring formed by R6 and R7 bonding to each other is a cyclic ether structure. The cyclic ether structure is preferably a 4- to 8-membered ring, more preferably a 5- to 7-membered ring.

[0133] Furthermore, R6 and R7 satisfy the relationship that the number of carbon atoms of the compound represented by Formula IV is 6 or more.

[0134] In Formula V, R8 and R9 each independently represent an alkyl group, a cycloalkyl group, or are bonded to each other to form a ring. L represents a single bond or an alkylene group.

[0135] As the alkyl group represented by R8 and R9, for example, an alkyl group having 6 to 12 carbon atoms is preferred, and an alkyl group having 6 to 10 carbon atoms is more preferred.

[0136] The cycloalkyl group represented by R8 and R9 is preferably a cycloalkyl group having 6 to 12 carbon atoms, and more preferably a cycloalkyl group having 6 to 10 carbon atoms.

[0137] The ring formed by bonding R8 and R9 to each other is a cyclic dione structure. The cyclic dione structure is preferably a 6- to 12-membered ring, and more preferably a 6- to 10-membered ring.

[0138] As the alkylene group represented by L, for example, an alkylene group having 1 to 12 carbon atoms is preferred, and an alkylene group having 1 to 10 carbon atoms is more preferred.

[0139] Furthermore, R8, R9 and L satisfy the relationship that the number of carbon atoms of the compound represented by Formula V is 6 or more.

[0140] Specific examples of the compound (B) include the following compounds.

[0141] [Chemical formula 3]

[0142]

[0143] In one embodiment, the treatment liquid of the present invention preferably contains Na, Ca and Fe, and the content of each atom is in the range of 0.01 mass ppt to 1000 mass ppb. Na, Ca and Fe are metal atoms mixed in various processes up to the synthesis of the treatment liquid of the present invention. When the concentration of each of these metal atoms is 1000 mass ppb or less, it is possible to suppress the situation where these metal atoms remain on the substrate as the core of the residual component during the treatment and become the cause of defects.

[0144] On the other hand, it is generally believed that the fewer these metal atoms, the better, but in the case of less than 0.01 mass ppt, a tendency for defects to increase again is confirmed. Although the mechanism may not be clear, it is inferred that when Na, Ca or Fe is removed from the substrate, it is removed in the form of being involved in compound (B) and / or compound (C) and in a manner that becomes a block of atoms to a certain extent. Therefore, it is believed that when Na, Ca or Fe is too little, the removal rate of compound (B) and / or compound (C) and Na, Ca or Fe deteriorates, and remains on the substrate and becomes the cause of defects.

[0145] The content rate of each atom of Na, Ca and Fe contained in the treatment liquid is more preferably 0.01 mass ppt to 500 mass ppb, and further preferably 0.05 mass ppt to 100 mass ppb.

[0146] In one embodiment of the treatment liquid of the present invention, the total content of metal particles when measured by SNP-ICP-MS (Single-Particle ICP-MS) is preferably 0.001 to 100 mass ppt, and more preferably 1 to 100 mass ppt, based on the total mass of the treatment liquid of the present invention.

[0147] Metal atoms contained as impurities in a semiconductor manufacturing process liquid are one of the main causes of defects in fine patterns or fine semiconductor elements. Therefore, it is believed that the less the amount of metal atoms contained in the semiconductor manufacturing process liquid, the better. However, the inventors have found that the amount of metal atoms contained in the process liquid is not necessarily related to the defect generation rate, and the defect generation rate has deviations.

[0148] According to the recently developed SNP-ICP-MS measurement, the amount of metal atoms present in the solution can be measured by dividing them into ionic metals and metal particles (non-ionic metals). Here, metal particles (non-ionic metals) refer to metal components that do not dissolve in the solution but exist as solids.

[0149] Until now, the amount of metal atoms contained in processing liquids for semiconductor manufacturing has generally been analyzed by ICP-MS, etc. Existing methods such as ICP-MS cannot identify ionic metals and metal particles (non-ionic metals) derived from metal atoms, and therefore the total mass of the metal atoms, i.e., the combined mass of the ionic metals and the particulate metals (non-ionic metals) (hereinafter also referred to as the "total metal amount", etc.) is quantified.

[0150] The inventors have conducted in-depth research on the effects of ionic metals and metal particles (non-ionic metals) on defects from metal atoms contained in the treatment solution, which can be identified and quantified by measurement using the SNP-ICP-MS method. As a result, it was found that the amount of metal particles (non-ionic metals) has a great influence on the generation of defects, and there is a correlation between the amount of metal particles (non-ionic metals) and the generation of defects.

[0151] In the treatment liquid of the present invention, the total content of the metal particles when measured by the SNP-ICP-MS method is particularly preferably 1 to 50 ppt by mass.

[0152] As devices that can be used in measurements using the SNP-ICP-MS method, in addition to the device used in the examples described later (NexION 350S manufactured by PerkinElmer, Inc.), for example, Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200) manufactured by Agilent Technologies, Ltd.; Agilent 8900 manufactured by Agilent Technologies, Ltd., etc.

[0153] Furthermore, in the embodiment of the present invention, a mixture of two or more of the above-mentioned treatment liquids of the present invention may be used as the treatment liquid of the present invention for various applications.

[0154] <Manufacturing of Processing Liquid for Semiconductor Manufacturing, etc.>

[0155] The treatment liquid of the present invention can be produced by a known method, for example, by reacting raw materials in the presence of a catalyst to synthesize compound (A) to obtain a crude liquid containing compound (A), and then purifying the crude liquid by, for example, filtration as described below.

[0156] The catalyst can be appropriately selected according to the compound (A). For example, sulfuric acid, HgSO4, NaNH2, Al(C2H5)3, Ipc2BH (Diisopinocampheylborane), a solid catalyst containing copper oxide-zinc oxide, a supported phosphoric acid catalyst, a supported copper catalyst, etc. can be cited.

[0157] In one embodiment, the method for producing a treatment liquid of the present invention preferably uses a compound containing at least any one selected from Al, B, S, N and K as a catalyst. In another embodiment, it is preferably used a compound containing at least any one selected from Al, B and S as a catalyst.

[0158] The raw materials used in the manufacture of the treatment liquid of the present invention are preferably raw materials that have been purified in advance by distillation, ion exchange, filtration, etc. For example, raw materials with a purity of 99% by mass or more, preferably 99.9% by mass or more. It is more preferred to use raw materials of high purity grade, and it is particularly preferred to use them after further purification. In order to obtain the remarkable effects of the present invention, it is important to use such high-purity raw materials.

[0159] In addition, the catalyst used in the method for producing the treatment liquid of the present invention is preferably a catalyst previously purified by distillation, ion exchange, filtration, etc. For example, a catalyst having a purity of 99 mass % or more, preferably a catalyst having a purity of 99.9 mass % or more, preferably a catalyst of a high purity grade.

[0160] Next, a production apparatus that can be preferably used to produce the treatment liquid of the present invention will be described.

[0161] 〔Manufacturing equipment〕

[0162] Figure 1This is a schematic diagram showing one form of a manufacturing apparatus that can be used in the method for manufacturing a treatment liquid involved in an embodiment of the present invention. The manufacturing apparatus 100 includes a tank 101, and the tank 101 includes a supply port 102 for supplying a cleaning liquid and / or an organic solvent (a crude liquid containing compound (A)) described later. The manufacturing apparatus 100 includes a filtering device 105, and the tank 101 and the filtering device 105 are connected by a supply line 109, and fluid (cleaning liquid, organic solvent, treatment liquid, etc.) can be transferred between the tank 101 and the filtering device 105. A valve 103 and a pump 104 are arranged in the supply line 109. Figure 1 In the embodiment, the production device 100 includes a tank 101 and a filtering device 105 , but the production device that can be used in the production method of the treatment liquid according to the embodiment of the present invention is not limited thereto.

[0163] In the manufacturing apparatus 100 , the fluid supplied from the supply port 102 flows into the filter device 105 via the valve 103 and the pump 104 . The fluid discharged from the filter device 105 is stored in the tank 101 via the circulation line 110 .

[0164] The manufacturing apparatus 100 includes a discharge unit 111 for discharging the treatment liquid to the circulation line 110. The discharge unit 111 includes a valve 107 and a container 108, and the manufactured treatment liquid can be stored in the container 108 by switching the valve 106 provided in the circulation line and the valve 107. In addition, the valve 107 is connected to a switchable pipeline 113, and the cleaning liquid after the circulation cleaning can be discharged to the outside of the manufacturing apparatus 100 through the pipeline 113. There are cases where the cleaning liquid after the circulation cleaning contains particles and metal impurities, etc. According to the manufacturing apparatus 100 including the pipeline 113 for discharging the cleaning liquid to the outside of the apparatus, a treatment liquid having a more excellent defect suppression performance can be obtained without contaminating the filling part of the container 108, etc.

[0165] Furthermore, the manufacturing apparatus 100 includes a cleaning liquid monitoring unit 112 in the circulation line 110. Figure 1 In the manufacturing device 100, the cleaning liquid monitoring unit 112 is provided in the circulation pipeline 110, but the manufacturing device that can be used in the manufacturing method of the treatment liquid involved in the embodiment of the present invention is not limited to this. The cleaning liquid monitoring unit 112 may be provided in the supply pipeline 109, or the cleaning liquid monitoring unit 112 may be provided in the supply pipeline 109 and the circulation pipeline 110. In addition, in the manufacturing device 100, the cleaning liquid monitoring unit 112 is directly provided in the circulation pipeline 110, but the manufacturing device that can be used in the manufacturing method of the treatment liquid involved in the embodiment of the present invention is not limited to this. The cleaning liquid monitoring unit may also be provided in a temporary storage tank (different from the tank 101) of the fluid not shown in the figure provided in the pipeline.

[0166] Figure 22 is a schematic diagram showing another form of a manufacturing apparatus that can be used in the manufacturing method of the treatment liquid involved in the embodiment of the present invention. The manufacturing apparatus 200 includes a tank 101 and a filtering device 105, and further includes a distillation tower 201, which is connected to the tank 101 through a pipeline 202, a pipeline 204, and a pipeline 203, and is arranged in a manner that a fluid can be transferred between the tank 101 and the pipeline. In addition, on the other hand, as a manufacturing apparatus that can be used in the manufacturing method of the treatment liquid involved in the embodiment of the present invention, it is not necessary to include the filtering device 105 and / or the distillation tower 201, and on the other hand, it is also possible to further include a reaction container connected to the distillation tower 201 through the pipeline 203.

[0167] In the manufacturing device 200, the fluid supplied to the distillation tower 201 via the pipeline 203 is distilled by the distillation tower 201. The distilled fluid is stored in the tank 101 via the pipeline 202. The supply pipeline 109 is provided with valves 103 and 206, and the fluid discharged from the tank 101 can flow into the filtering device 105 by switching with the valve 205 provided in the pipeline 204.

[0168] In the production apparatus 200, the fluid discharged from the tank 101 can be made to flow again into the distillation column 201. In this case, the fluid flows from the pipe 204 through the valve 207 and the pipe 203 into the distillation column 201 by switching the valves 103, 206, and 205.

[0169] The material of the liquid contact part (the definition of the liquid contact part will be described later) of the manufacturing device is not particularly limited, but it is preferably formed of at least one selected from the group consisting of non-metallic materials and electrolytically polished metal materials in order to obtain a treatment liquid with more excellent defect suppression performance. In addition, in this specification, the so-called "liquid contact part" refers to a part that has the possibility of contact with the fluid (for example, the inner surface of the tank, the liquid delivery pump, the baffle, the seal, the O-ring, and the inner surface of the pipeline, etc.) and the area with a thickness of 100nm from the surface.

[0170] The non-metal material is not particularly limited, but is preferably a polyethylene resin, a polypropylene resin, a polyethylene-polypropylene resin, and a fluorine-containing resin material. From the viewpoint of less elution of metal atoms, a fluorine-containing resin material is preferred.

[0171] As the above-mentioned fluorine-containing resin, perfluororesin and the like can be listed, and tetrafluoroethylene resin (PTFE), tetrafluoroethylene·perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), tetrafluoroethylene-ethylene copolymer resin (ETFE), chlorotrifluoroethylene-ethylene copolymer resin (ECTFE), vinylidene fluoride resin (PVDF), chlorotrifluoroethylene copolymer resin (PCTFE), polyvinyl fluoride resin (PVF), etc. can be listed.

[0172] As particularly preferred fluorine-containing resins, there can be mentioned tetrafluoroethylene resins, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers, and tetrafluoroethylene-hexafluoropropylene copolymer resins.

[0173] The metal material is not particularly limited, and a known material can be used.

[0174] As the metal material, for example, the total content of chromium and nickel relative to the total mass of the metal material can be listed as a metal material exceeding 25 mass%, wherein more preferably 30 mass% or more. There is no particular upper limit to the total content of chromium and nickel in the metal material, but it is usually preferably 90 mass% or less.

[0175] Examples of the metal material include stainless steel, carbon steel, alloy steel, nickel-chromium-molybdenum steel, chrome steel, chrome-molybdenum steel, manganese steel, and nickel-chromium alloys.

[0176] There is no particular limitation on stainless steel, and known stainless steel can be used. 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 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 listed.

[0177] The nickel-chromium alloy is not particularly limited, and a known nickel-chromium alloy can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75% by mass and a chromium content of 1 to 30% by mass is preferred.

[0178] Examples of nickel-chromium alloys include Hastelloy (trade name, the same below), Monel copper-nickel alloy (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 %) are included.

[0179] Furthermore, in addition to the above alloys, the nickel-chromium alloy may further contain boron, silicon, tungsten, molybdenum, copper, cobalt, and the like as necessary.

[0180] 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.

[0181] It is speculated that the chromium content in the passivation layer on the surface of the metal material becomes higher than the chromium content in the parent phase due to electrolytic polishing. Therefore, it is speculated that metal impurities containing metal atoms are less likely to flow out into the organic solvent from the distillation tower whose liquid contact part is formed by the electrolytically polished metal material, so that a distilled organic solvent with a reduced impurity content can be obtained.

[0182] 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 polishing abrasive grains used for the final processing of the polishing is not particularly limited, but is preferably less than #400 in terms of the fact that the surface concavity and convexity of the metal material is more likely to become smaller. In addition, the polishing is preferably performed before the electrolytic polishing.

[0183] In terms of obtaining a treatment liquid with better defect suppression performance, the liquid contact part is preferably formed of electrolytically polished stainless steel. In particular, when the manufacturing device is equipped with a tank, the liquid contact part of the tank is more preferably formed of electrolytically polished stainless steel. There is no particular restriction on the mass ratio of the Cr content in the liquid contact part to the Fe content (hereinafter also referred to as "Cr / Fe"), and it is usually preferably 0.5 to 4. Among them, in terms of the fact that metal impurities and / or organic impurities are more difficult to dissolve into the treatment liquid, it is more preferably greater than 0.5 and less than 3.5, and more preferably greater than 0.7 and less than 3.0. If Cr / Fe exceeds 0.5, the dissolution of metal from the tank can be suppressed. If Cr / Fe is less than 3.5, it is difficult to cause peeling of the liquid contact part that causes particles.

[0184] The method for adjusting Cr / Fe in the metal material is not particularly limited, and examples thereof include a method of adjusting the content of Cr atoms in the metal material and a method of making the chromium content in the passivation layer of the polished surface greater than the chromium content in the parent phase by electrolytic polishing.

[0185] The above-mentioned metal material may be a metal material to which coating technology is applied.

[0186] Coating technology is roughly divided into three types: metal coating (various electroplating), inorganic coating (various chemical conversion treatments, glass, concrete, ceramics, etc.) and organic coating (anti-rust oil, paint, rubber, plastic, etc.), and any one of them can be used.

[0187] Preferred coating techniques include surface treatment using rust preventive oil, rust preventive agent, corrosion inhibitor, chelate compound, strippable plastic, and lining agent.

[0188] Among them, as a coating technology, surface treatment using corrosion inhibitors, chelate compounds and lining agents is preferred. Here, as corrosion inhibitors, various chromates, nitrites, silicates, phosphates, carboxylic acids (oleic acid, dimer acid, cyclopentane acid, etc.), carboxylic acid metal soaps, sulfonates, amine salts and esters (glycerides or phosphates of higher fatty acids) can be listed. As chelate compounds, ethylenediaminetetraacetic acid, gluconic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, etc. can be listed. As lining agents, fluororesin lining agents, etc. can be listed. Particularly preferred is treatment using phosphates or fluororesin lining agents.

[0189] By providing the manufacturing apparatus with the filter device 105, it is easy to obtain a treatment liquid having a more excellent defect suppression performance. The filter component contained in the filter device 105 is not particularly limited, and is preferably at least one selected from the group consisting of a filter having a particle size of 20 nm or less and a metal ion adsorption filter, and more preferably a filter having a particle size of 20 nm or less and a metal ion adsorption filter.

[0190] ·Filters that remove particles with a diameter of less than 20 nm

[0191] The filter for removing particles having a diameter of 20 nm or less has a function of efficiently removing particles having a diameter of 20 nm or more from the organic solvent or the like which is the raw material of the treatment liquid.

[0192] The particle size of the filter is preferably 1 to 15 nm, more preferably 1 to 12 nm. When the particle size is 15 nm or less, finer particles can be removed, and when the particle size is 1 nm or more, the filtration efficiency is improved.

[0193] Here, the particle removal diameter refers to the minimum size of particles that can be removed by the filter. For example, when the particle removal diameter of the filter is 20 nm, particles with a diameter of 20 nm or more can be removed.

[0194] As the material of the filter, for example, nylons such as 6-nylon and 6,6-nylon, polyethylene, polypropylene, polystyrene, polyimide, polyamide-imide and fluororesin can be listed. Polyimide and / or polyamide-imide can also be a compound having at least one selected from the group including carboxyl, salt-type carboxyl and -NH-bond. Regarding solvent resistance, fluororesin, polyimide and / or polyamide-imide are excellent. In addition, from the viewpoint of adsorption of metal ions, nylons such as 6-nylon and 6,6-nylon are particularly preferably.

[0195] The filter device 105 may also contain a plurality of the above-mentioned filters. When the filter device 105 contains a plurality of filters, there is no particular limitation on the other filters, and preferably a filter having a particle size of 50 nm or more (for example, a microfiltration membrane for removing microparticles having a pore size of 50 nm or more). In the case where there are microparticles in addition to colloided impurities, especially colloided impurities containing metal atoms such as iron or aluminum, before filtering with a filter having a particle size of 20 nm or less (for example, a microfiltration membrane having a pore size of 20 nm or less), the filter having a particle size of 50 nm or more (for example, a microfiltration membrane for removing microparticles having a pore size of 50 nm or more) is used to filter the purified material, thereby improving the filtration efficiency of the filter having a particle size of 20 nm or less (for example, a microfiltration membrane having a pore size of 20 nm or less), and further improving the particle removal performance.

[0196] Metal ion adsorption filter

[0197] The filtering device 105 preferably includes a metal ion adsorption filter.

[0198] The metal ion adsorption filter is not particularly limited, and examples thereof include known metal ion adsorption filters.

[0199] Among them, the metal ion adsorption filter is preferably a filter capable of ion exchange. Here, the metal ion to be adsorbed is not particularly limited, but from the point of view of being a cause of defects in semiconductor devices, it is preferably a metal ion containing one selected from the group consisting of Fe, Cr, Ni, and Pb, and more preferably a metal ion containing Fe, Cr, Ni, and Pb respectively.

[0200] From the viewpoint of improving the metal ion adsorption performance, the metal ion adsorption filter preferably contains an acid group on the surface. Examples of the acid group include a sulfonic group and a carboxyl group.

[0201] Examples of the base material (material) constituting the metal ion adsorption filter include cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, and fluororesin, etc. Nylon is particularly preferred from the viewpoint of the efficiency of adsorbing metal ions.

[0202] In addition, the metal ion adsorption filter may also be composed of a material containing polyimide and / or polyamide-imide. As the metal ion adsorption filter, for example, polyimide and / or polyamide-imide porous membranes described in Japanese Patent Application Publication No. 2016-155121 (JP 2016-155121) can be cited.

[0203] The polyimide and / or polyamideimide porous membrane may also be a porous membrane containing at least one selected from the group consisting of a carboxyl group, a salt-type carboxyl group, and an -NH- bond. If the metal ion adsorption filter contains a fluororesin, polyimide and / or polyamideimide, it has more excellent solvent resistance.

[0204] Organic impurities adsorption filter

[0205] The filtering device 105 may further include an organic impurity adsorption filter.

[0206] The organic impurity adsorption filter is not particularly limited, and a known organic impurity adsorption filter may be used.

[0207] Among them, in terms of improving the adsorption performance of organic impurities, as an organic impurity adsorption filter, it is preferred that the surface has an organic skeleton that can interact with organic impurities (in other words, the surface is modified by an organic skeleton that can interact with organic impurities). As an organic skeleton that can interact with organic impurities, for example, a chemical structure that reacts with organic impurities and can capture organic impurities into an organic impurity adsorption filter can be cited. More specifically, in the case of containing normal long-chain alkyl alcohol (structural isomers when using 1-long-chain alkyl alcohol as an organic solvent) as an organic impurity, an alkyl group can be cited as an organic skeleton. In addition, in the case of containing butylated hydroxytoluene (BHT) as an organic impurity, a phenyl group can be cited as an organic skeleton.

[0208] Examples of the substrate (material) constituting the organic impurity adsorption filter include cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, and fluororesin on which activated carbon is supported.

[0209] In addition, as an organic impurity adsorption filter, a filter in which activated carbon is fixed to a nonwoven fabric as described in Japanese Patent Application Laid-Open Nos. 2002-273123 and 2013-150979 can also be used.

[0210] As the organic impurity adsorption filter, in addition to the chemical adsorption described above (adsorption using an organic impurity adsorption filter having an organic skeleton on the surface capable of interacting with organic impurities), a physical adsorption method can also be applied.

[0211] For example, in the case of containing BHT as an organic impurity, the structure of BHT is larger than (=1nm). Therefore, by using an organic impurity adsorption filter with a pore size of 1nm, BHT cannot pass through the pores of the filter. That is, BHT is physically captured by the filter and is therefore removed from the purified material. In this way, the removal of organic impurities can be applied not only to chemical interactions but also to physical removal methods. In this case, a filter with a pore size of 3nm or more is used as a "particle removal filter", and a filter with a pore size of less than 3nm is used as an "organic impurity adsorption filter".

[0212] Although it is repeatedly described, when using filters, different filters may be combined. In this case, filtering using the first filter may be performed only once or twice or more. When filtering is performed twice or more by combining different filters, the filters may be of the same type or different types, preferably different types. Typically, the first filter and the second filter preferably differ in at least one of pore size and constituent material.

[0213] The pore size of the filtration after the second time is preferably the same as the pore size of the first filtration, or smaller than the pore size of the first filtration. In addition, the first filter with different pore sizes can also be combined within the above range. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, it can be selected from various filters provided by Nihon Pall Ltd., Advantec Toyo Kaisha, Ltd., Nihon Entegris KK (formerly Nippon Mykrolis Corporation) or KITZ MICROFILTER CORPORATION. In addition, it is also possible to use a "P-nylon filter (pore size 0.02μm, critical surface tension 77mN / m)" made of polyamide; (made by Nihon Pall Ltd.), a "PE·clean filter (pore size 0.02μm)" made of high-density polyethylene; (made by Nihon Pall Ltd.) and a "PE·clean filter (pore size 0.01μm)" made of high-density polyethylene; (made by Nihon Pall Ltd.).

[0214] The manufacturing method of the treatment liquid involved in the embodiment of the present invention may also include a step of cleaning the manufacturing device with a cleaning liquid. In this method, the cleaning liquid is supplied from the supply port 102 of the tank 101. The supply amount of the cleaning liquid is not particularly limited, and it is preferably an amount that can fully clean the liquid contact part of the tank 101, and the capacity of the supplied cleaning liquid is preferably 30% by volume or more relative to the capacity of the tank 101. When the cleaning liquid is supplied from the supply port 102, the valve 103 can be closed or opened. In terms of making it easier to clean the tank 101, it is preferred to close the valve 103 when the cleaning liquid is supplied from the supply port 102.

[0215] The cleaning liquid supplied to the tank 101 can be directly transferred in the manufacturing device, or it can be transferred in the manufacturing device (for example, through the supply pipeline 109) after cleaning the tank 101. There is no particular limitation on the method of using the cleaning liquid to clean the tank 101. For example, a method of cleaning by rotating an unillustrated stirring impeller provided in the tank 101 can be cited. There is no particular limitation on the time for cleaning the tank with the cleaning liquid. It can be appropriately selected according to the material of the liquid receiving part of the tank 101, the type of the processing liquid manufactured, the possibility of contamination, etc. It is usually preferably about 0.1 seconds to 48 hours. In addition, in the case of cleaning only the tank 101, the cleaning liquid after cleaning can also be discharged from an unillustrated outlet provided at the bottom of the tank, for example.

[0216] There is no particular limitation on the method of using the cleaning liquid to clean the supply line 109 and the like of the manufacturing device 100, but a method (hereinafter also referred to as "circulation cleaning") is preferably used in which the pump 104 is operated after the valves 103 and 106 are opened and the valve 107 is closed, so that the cleaning liquid is circulated in the manufacturing device through the supply line 109 and the circulation line 110. By performing the above-mentioned operation, foreign matter and the like attached to the liquid contact parts such as the tank 101, the filter device 105 and the supply line 109 can be more efficiently dispersed and / or more efficiently dissolved by the cleaning liquid while the cleaning liquid is transferred.

[0217] In particular, when the manufacturing apparatus is equipped with a filtering device, the cleaning method is more preferably circulation cleaning. Figure 1 An example of circulation cleaning is described below. First, the cleaning liquid supplied from the tank 101 to the manufacturing device through the valve 103 is returned to the tank 101 (circulated) again through the supply line 109 (and through the filter device 105, the circulation line 110 and the valve 106). At this time, the cleaning liquid is filtered by the filter device 105 to remove particles dissolved and dispersed in the cleaning liquid, which can further improve the cleaning effect.

[0218] As another form of the cleaning method, for example, the following method may be used: after opening valves 103 and 107 and closing valve 106, pump 104 is operated to allow the cleaning liquid supplied from supply port 102 of tank 101 to flow into filter device 105 through valve 103 and pump 104, and then the cleaning liquid is discharged to the outside of the manufacturing device through valve 107 without circulation (hereinafter, this method is also referred to as "batch cleaning" in this specification). In this case, the cleaning liquid may be intermittently supplied to the manufacturing device in a fixed amount as described above, or may be continuously supplied to the manufacturing device.

[0219] (Cleaning fluid)

[0220] As described above, the cleaning liquid used in the preliminary cleaning is not particularly limited, and a known cleaning liquid can be used.

[0221] Examples of the cleaning liquid include water, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactates, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates.

[0222] Moreover, as a cleaning liquid, the cleaning liquid described in Japanese Unexamined Patent Publication No. 2016-57614, Japanese Unexamined Patent Publication No. 2014-219664, Japanese Unexamined Patent Publication No. 2016-138219, and Japanese Unexamined Patent Publication No. 2015-135379 may be used, for example.

[0223] As the cleaning liquid, it is preferred to contain PGME (propylene glycol monomethyl ether), CyPe (cyclopentanone), nBA (butyl acetate), PGMEA (propylene glycol monomethyl ether acetate), CyHx (cyclohexanone), EL (ethyl lactate), HBM (methyl 2-hydroxyisobutyrate), DBCPN (cyclopentanone dimethyl acetal), GBL (γ-butyrolactone), DMSO (dimethyl sulfoxide), EC (ethylene carbonate), PC (propylene carbonate), NMP (1-methyl-2-pyrrolidone), iAA (isoamyl acetate), IPA (isopropyl alcohol) , MEK (methyl ethyl ketone) and MIBC (4-methyl-2-pentanol), more preferably contains at least one selected from the group including PGMEA, NMP, PGME, nBA, PC, CyHx, GBL, MIBC, EL, DMSO, iAA, MEK, PC and CyPe, and further preferably consists of at least one selected from the group including PGMEA, NMP, PGME, nBA, PC, CyHx, GBL, MIBC, EL, DMSO, iAA, MEK, PC and CyPe.

[0224] In addition, the cleaning liquid may be used alone or in combination of two or more. In addition, the treatment liquid of the present invention may be used as the cleaning liquid.

[0225] [Method for adjusting metal content]

[0226] The treatment liquid of the present invention preferably has an ion concentration of Cr, Co, Cu, Pb, Li, Mg, Mn, Ni, K, Ag and Zn of 1 ppm (parts per million) or less, more preferably 1 ppb or less. In particular, it is further preferred that the concentration is at the ppt level (the above concentrations are all based on mass), and it is particularly preferred that the treatment liquid contains substantially no ions.

[0227] The adjustment of the metal content in the treatment liquid of the present invention can be carried out, for example, by repeating distillation or filtration, filtration using ion exchange resins, adsorption purification, etc. in at least one stage of the stage of preparing the raw materials used in the treatment liquid and the stage after the treatment liquid is prepared, and fully purifying.

[0228] Here, the method for adjusting the metal content (hereinafter also referred to as "metal concentration reduction method") is not particularly limited, and examples include adsorption purification using silicon carbide described in International Publication No. W012 / 043496, and further examples of combined distillation or filter filtration, and filtration using ion exchange resins to fully purify can be listed as preferred forms.

[0229] From the viewpoint of obtaining the effect of the present invention, the method for adjusting the metal content is particularly preferably carried out at the stage of the raw materials used when manufacturing the treatment solution. In addition, the raw materials preferably use specific metal atoms or inorganic ions such as sulfate ions, chloride ions or nitrate ions, and raw materials of the level of metal ions described later.

[0230] As another method related to the method of reducing the metal concentration, it is possible to use a container with little elution of impurities as described below with respect to the storage container for storing the treatment liquid of the present invention as a "container" for storing the raw materials used in the production of the treatment liquid. In addition, the following method can also be mentioned: lining the inner wall of the pipe with a fluorine-based resin so that the metal component does not dissolve from the "pipe" when preparing the treatment liquid.

[0231] [Impurities and coarse particles]

[0232] Furthermore, the treatment liquid of the present invention preferably contains substantially no coarse particles.

[0233] In addition, the so-called coarse particles contained in the treatment liquid refer to particles such as dust, dust, organic solid substances, inorganic solid substances, etc. contained as impurities in the raw materials or particles such as dust, dust, organic solid substances, inorganic solid substances, etc. introduced as contaminants during the preparation of the treatment liquid, which are equivalent to particles that are not dissolved in the final treatment liquid and exist in the form of particles. The amount of coarse particles present in the treatment liquid can be measured in the liquid phase using a commercially available measuring device in a light scattering liquid particle measuring method using a laser as a light source.

[0234] [Kit and Concentrate]

[0235] The treatment solution of the present invention can also be set as a kit to which other raw materials are added separately. In this case, as other raw materials added separately during use, in addition to solvents such as water or organic solvents, other compounds can also be mixed and used according to the purpose. From the viewpoint of significantly obtaining the effect of the present invention, in the solvent that can be used at this time, if the respective content ratios of Na, Ca or Fe contained in the solvent are in the range of the specific values ​​of the present invention described above, the desired effect of the present invention can be significantly obtained.

[0236] <Container>

[0237] The treatment solution of the present invention (regardless of whether it is a kit) can be filled into any container for storage, transportation and use as long as corrosion resistance is not a problem. The container is preferably a container for semiconductor use with high cleanliness and little dissolution of impurities. As containers that can be used, the "clean bottle (cleanbottle)" series of AICELLO CORPORATION, the "pure bottle (purebottle)" of KODAMA PLASTICS Co., Ltd., etc. can be listed, but it is not limited to these.

[0238] The liquid contact portion of the container is preferably formed of a non-metallic material or stainless steel.

[0239] Examples of the non-metallic material include the materials exemplified as the non-metallic material used in the liquid contact part of the above-mentioned distillation column. In particular, among the above-mentioned materials, the occurrence of the disadvantage of elution of oligomers of ethylene or propylene can be suppressed compared to the case where a container having a liquid contact part made of fluororesin or a container having a liquid contact part made of polyethylene resin, polypropylene resin or polyethylene-polypropylene resin is used.

[0240] As a specific example of such a container whose liquid contact part is a fluororesin, for example, a FluoroPure PFA composite drum manufactured by Entegris, Inc. can be cited. In addition, containers described in page 4 of JP-A-3-502677, page 3 of International Publication No. 2004 / 016526, and pages 9 and 16 of International Publication No. 99 / 46309 can also be used. In addition, when the liquid contact part is made of a non-metallic material, it is preferable to suppress dissolution into the non-metallic material.

[0241] The container preferably has a liquid contact portion that contacts the treatment liquid made of stainless steel, more preferably electrolytically polished stainless steel.

[0242] When the processing liquid is stored in the container, it is more difficult for the impurity metals and / or organic impurities to be dissolved into the processing liquid stored in the container.

[0243] The above-mentioned stainless steel has been described as a material for the liquid contact part of the distillation tower, and the same also applies to the electrolytically polished stainless steel.

[0244] The Cr / Fe ratio in the stainless steel forming the liquid contact portion of the above-mentioned container has been described as the Cr / Fe ratio in the liquid contact portion of the tank.

[0245] These containers are preferably cleaned before filling. The liquid used for cleaning is not particularly limited, but preferably has a metal content of less than 0.001 mass ppt (parts per trillion). In addition, depending on the application, if it is a liquid in which the metal content is set to the above range by purifying other organic solvents other than water described later, or the treatment liquid of the present invention itself, or a liquid obtained by diluting the treatment liquid of the present invention, or a liquid containing at least one of the compounds added to the treatment liquid of the present invention, then the effect of the present invention can be significantly obtained.

[0246] The treatment liquid may be transported and stored in a container such as a gallon bottle or a coating bottle after production. The gallon bottle may be made of glass or other materials.

[0247] In order to prevent the change of the components in the solution during storage, the container may be replaced with an inert gas (nitrogen or argon, etc.) with a purity of 99.99995% by volume or more. A gas with a low water content is particularly preferred. In addition, the temperature may be controlled within the range of -20°C to 30°C during transportation and storage to prevent deterioration.

[0248] Furthermore, before cleaning the container, it is preferable to remove foreign matter adhering to the cover by cleaning the cover of various containers with an acid or an organic solvent, thereby preventing foreign matter from entering through the cover.

[0249] [water]

[0250] The water used in conjunction with the present invention, for example, water that can be used in the manufacturing process of the treatment liquid of the present invention, water that can be used in the pattern forming process of the present invention, water that can be used in the cleaning of the storage container of the treatment liquid of the present invention, the component determination of the treatment liquid of the present invention or the determination of the defect suppression performance and lithography performance evaluation involved in the effect of the present invention is preferably ultrapure water used in semiconductor manufacturing. In addition, it is more preferred to use water that further purifies the ultrapure water and reduces inorganic anions or metal ions. The purification method is not particularly limited, and is preferably purified using a filter membrane or an ion exchange membrane or purified by distillation. In addition, for example, it is preferably purified by the method described in Japanese Patent Publication No. 2007-254168.

[0251] In one form, the water preferably has a metal content of less than 0.001 parts per trillion (ppt).

[0252] [Cleaning room]

[0253] The adjustment of the treatment liquid of the present invention, or the operation including opening and / or cleaning of the storage container, filling of the treatment liquid, or the treatment analysis and measurement are preferably performed in a clean room. The clean room preferably meets the 14644-1 clean room standard. Preferably, it meets any one of ISO Class 1, ISO Class 2, ISO Class 3, and ISO Class 4, more preferably meets ISO Class 1 and ISO Class 2, and particularly preferably ISO Class 1.

[0254] [Use of treatment fluid]

[0255] The processing liquid of the present invention can be preferably used for semiconductor manufacturing purposes. Specifically, in the manufacturing process of semiconductor devices including photolithography process, etching process, ion implantation process and stripping process, it is used to treat organic matter after each process is completed or before transferring to the next process. Specifically, it can be preferably used as a pre-wetting liquid, developer, rinse liquid and stripping liquid. For example, it can also be used for rinsing the edge line of the semiconductor substrate before and after the resist coating.

[0256] Furthermore, the above-mentioned processing liquid can also be used as a cleaning liquid for an apparatus for producing various processing liquids used in semiconductor manufacturing applications.

[0257] Furthermore, the above-mentioned treatment liquid can also be used as a diluent of the resin contained in the resist liquid (described later), that is, it can also be used as a solvent contained in the actinic ray-sensitive or radiation-sensitive composition.

[0258] Furthermore, the processing liquid can be preferably used for purposes other than semiconductor manufacturing, and can also be used as a developer or rinser for polyimide, sensor resist, lens resist, and the like.

[0259] In addition, the processing liquid can also be used as a solvent for medical purposes or cleaning purposes, and can be preferably used for cleaning containers, pipes, substrates (for example, wafers, glass, etc.), etc.

[0260] <Pattern Formation Method>

[0261] The processing liquid of the present invention is basically a processing liquid used as a developer, rinse liquid, pre-wet liquid, stripping liquid, etc. in a semiconductor device manufacturing method. In one embodiment, it is preferably used as a developer, rinse liquid or pre-wet liquid in a pattern forming method included in the semiconductor device manufacturing method.

[0262] The pattern forming method of the present invention includes: a resist film forming step of coating an actinic ray or radiation-sensitive composition (hereinafter also referred to as an "resist composition") on a substrate to form an actinic ray or radiation-sensitive film (hereinafter also referred to as a "resist film"); an exposure step of exposing the above-mentioned resist film; and a treatment step of treating the substrate before coating the above-mentioned resist composition or the above-mentioned resist film after exposure with the above-mentioned treatment liquid.

[0263] In the pattern forming method of the present invention, the processing liquid of the present invention can be used as any one of a developer, a rinse liquid and a pre-wet liquid, preferably used as any two of the developer, the rinse liquid and the pre-wet liquid, and more preferably used as a developer, the rinse liquid and the pre-wet liquid.

[0264] Hereinafter, each step included in the pattern forming method of the present invention will be described. In addition, as an example of a treatment step using the treatment liquid of the present invention, a pre-wetting step, a developing step, and a rinsing step will be described.

[0265] <Prewetting process>

[0266] The pattern forming method of the present invention may also include a pre-wetting step of pre-coating a pre-wetting liquid on the substrate to improve coating properties before the step of forming a resist film using an actinic ray-sensitive or radiation-sensitive composition. For example, the pre-wetting step is described in Japanese Patent Application Publication No. 2014-220301, and is cited therein.

[0267] <Resist Film Formation Step>

[0268] The resist film forming step is a step of forming a resist film using an actinic ray-sensitive or radiation-sensitive composition, and can be performed, for example, by the following method.

[0269] In order to form a resist film (actinic ray or radiation-sensitive composition film) on a substrate using an actinic ray or radiation-sensitive composition, each component described below is dissolved in a solvent to prepare an actinic ray or radiation-sensitive composition, and after filtering through a filter as needed, it is applied to the substrate. As the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon with a pore size of 0.1 μm or less is preferred, 0.05 μm or less is more preferred, and 0.03 μm or less is further preferred.

[0270] The photosensitive ray or radiation-sensitive resin composition is applied to a substrate (e.g., silicon, silicon dioxide coating) for manufacturing integrated circuit elements by a suitable coating method such as a spinner. Then, it is dried to form a resist film. Various base films (inorganic films, organic films, anti-reflective films) can also be formed under the resist film as needed.

[0271] As a drying method, a method of drying by heating is generally used. Heating can be performed by a mechanism provided in a common exposure / developing machine, or can be performed using a hot plate or the like.

[0272] The heating temperature is preferably 80 to 180° C., more preferably 80 to 150° C., further preferably 80 to 140° C., and particularly preferably 80 to 130° C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and further preferably 60 to 600 seconds.

[0273] The film thickness of the resist film is usually 200 nm or less, preferably 100 nm or less.

[0274] For example, in order to analyze a 1:1 line and space pattern with a size of 30 nm or less, the thickness of the formed resist film is preferably 50 nm or less. If the film thickness is 50 nm or less, it is more difficult to cause pattern collapse when applying the development process described later, thereby obtaining better resolution performance.

[0275] As the range of film thickness, the range of 15nm to 45nm is more preferred. If the film thickness is 15nm or more, sufficient etching resistance can be obtained. As the range of film thickness, 15nm to 40nm is more preferred. If the film thickness is within this range, both etching resistance and better resolution performance can be satisfied.

[0276] In addition, in the pattern forming method of the present invention, an upper film (top coating film) can also be formed on the upper layer of the resist film. The upper film can be formed using, for example, an upper film forming composition containing a hydrophobic resin, an acid generator, and an alkaline compound. The upper film and the upper film forming composition are described below.

[0277] <Exposure Process>

[0278] The exposure step is a step of exposing the above-mentioned resist film to light, and can be performed, for example, by the following method.

[0279] The resist film formed as described above is irradiated with actinic rays or radiation through a predetermined mask. In the case of electron beam irradiation, drawing is usually performed without using a mask (direct drawing).

[0280] The actinic ray or radiation is not particularly limited, and examples thereof include KrF excimer laser, ArF excimer laser, EUV light (Extreme Ultra Violet), electron beam (EB), etc. The exposure may be liquid immersion exposure.

[0281] <Bake>

[0282] In the pattern forming method of the present invention, it is preferred to perform baking (heating) after exposure and before development. Baking promotes the reaction of the exposed portion, thereby further improving the sensitivity and pattern shape.

[0283] The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C.

[0284] The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0285] Heating can be performed by a mechanism included in a general exposure / developing machine, or can be performed using a heating plate or the like.

[0286] <Development Process>

[0287] The development step is a step of developing the exposed resist film with a developer.

[0288] As a developing method, for example, the following methods can be applied: a method of immersing a substrate in a tank filled with a developer for a certain period of time (immersion method); a method of developing by utilizing surface tension to deposit the developer on the surface of the substrate and allowing it to remain stationary for a certain period of time (spin immersion method); a method of spraying the developer onto the surface of the substrate (spray method); a method of continuously spraying the developer on the substrate rotating at a constant speed while scanning a developer spray nozzle at a constant speed (dynamic distribution method), etc.

[0289] Furthermore, after the step of developing, a step of stopping the development while replacing the solvent with another solvent may be performed.

[0290] The development time is not particularly limited as long as it is a time for the resin in the unexposed portion to fully dissolve, but is usually 10 to 300 seconds, preferably 20 to 120 seconds.

[0291] The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.

[0292] As the developer used in the development step, the above-mentioned treatment solution is preferably used. The developer is as described above. In addition to development using the treatment solution, development using an alkali developer (so-called double development) may also be performed.

[0293] <Rinsing process>

[0294] The rinsing step is a step of performing cleaning (rinsing) with a rinsing liquid after the above-mentioned development step.

[0295] In the rinsing step, the developed wafer is cleaned using a rinsing liquid.

[0296] There is no particular limitation on the cleaning method, and the following methods may be applied: a method of continuously spraying a rinsing liquid onto a substrate rotating at a certain speed (rotary spraying method); a method of immersing a substrate in a tank filled with a rinsing liquid for a certain period of time (immersion method); a method of spraying the rinsing liquid onto the surface of the substrate (spraying method), etc. Among them, it is preferred to use a rotary spraying method for cleaning, and after cleaning, the substrate is rotated at a rotation speed of 2000rpm to 4000rpm, and the rinsing liquid is removed from the substrate.

[0297] The rinsing time is not particularly limited, but is usually 10 to 300 seconds, preferably 10 to 180 seconds, and most preferably 20 to 120 seconds.

[0298] The temperature of the rinse liquid is preferably 0 to 50°C, more preferably 15 to 35°C.

[0299] Furthermore, after the development process or the rinse process, a process of removing the developing solution or the rinse solution adhering to the pattern using a supercritical fluid can be performed.

[0300] Furthermore, after developing or rinsing or using a supercritical fluid, a heat treatment for removing the solvent remaining in the pattern can be performed. As long as a good resist pattern can be obtained, the heating temperature is not particularly limited, and is usually 40 to 160° C. The heating temperature is preferably 50 to 150° C., and most preferably 50 to 110° C. Regarding the heating time, as long as a good resist pattern can be obtained, it is not particularly limited, and is usually 15 to 300 seconds, and preferably 15 to 180 seconds.

[0301] As the rinse liquid, it is preferable to use the above-mentioned treatment liquid. The description of the rinse liquid is as described above.

[0302] The pattern forming method of the present invention is as described above. As long as any one of the developer, rinse liquid and pre-wet liquid is the processing liquid of the above-mentioned present invention, any two or more of the developer, rinse liquid and pre-wet liquid can be the processing liquid of the present invention, or three of the developer, rinse liquid and pre-wet liquid can be the processing liquid of the present invention.

[0303] The processing liquid and the actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method of the present invention preferably satisfy the following relationship in one embodiment.

[0304] That is, it is preferred to use an actinic ray or radiation sensitive resin composition and the treatment liquid of the present invention that satisfy the relationship that the dissolution rate of the actinic ray or radiation sensitive film formed using the actinic ray or radiation sensitive resin composition in the treatment liquid of the present invention is 0.0016 to 0.33 nm / sec.

[0305] Here, the so-called dissolution rate of the actinic ray or radiation-sensitive film with respect to the processing liquid of the present invention refers to the film thickness reduction rate when the actinic ray or radiation-sensitive film is immersed in the processing liquid of the present invention after film formation, and in the present invention, it is set to the dissolution rate at 23° C. The dissolution rate is more preferably 0.0016 to 0.16 nm / sec, and further preferably 0.0016 to 0.08 nm / sec.

[0306] <Actylene ray or radiation-sensitive composition (resist composition)>

[0307] Next, the actinic ray-sensitive or radiation-sensitive composition preferably used in combination with the treatment liquid of the present invention will be described in detail.

[0308] (A) Resin

[0309] The actinic ray-sensitive or radiation-sensitive resin composition preferably used in combination with the treatment liquid of the present invention preferably contains a resin (A). The resin (A) contains at least (i) a repeating unit having a group that decomposes by the action of an acid to generate a carboxyl group (and further, may contain a repeating unit having a phenolic hydroxyl group), or contains at least (ii) a repeating unit having a phenolic hydroxyl group.

[0310] Furthermore, when a repeating unit having a group that generates a carboxyl group when decomposed by the action of an acid is included, the solubility in an alkaline developer increases due to the action of the acid, and the solubility in an organic solvent decreases.

[0311] Examples of the repeating unit having a phenolic hydroxyl group contained in the resin (A) include repeating units represented by the following general formula (I).

[0312] [Chemical formula 4]

[0313]

[0314] In the formula,

[0315] R 41 , R 42 and R 43 Each independently represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. 42 It can be bonded with Ar4 to form a ring. In this case, R 42 represents a single bond or an alkylene group.

[0316] X4 represents a single bond, -COO- or -CONR 64 -, R 64 represents a hydrogen atom or an alkyl group.

[0317] L4 represents a single bond or an alkylene group.

[0318] Ar4 represents an (n+1)-valent aromatic ring group, and in the presence of R 42 When they are bonded to form a ring, they represent an (n+2)-valent aromatic ring group.

[0319] n represents an integer of 1-5.

[0320] As R in the general formula (I) 41 , R 42 , R 43 The alkyl group may preferably be an alkyl group having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, which may have a substituent; more preferably, an alkyl group having 8 or less carbon atoms; and particularly preferably, an alkyl group having 3 or less carbon atoms.

[0321] As R in the general formula (I) 41 , R 42 , R 43 The cycloalkyl group may be monocyclic or polycyclic. Preferred examples include monocyclic cycloalkyl groups having 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, and cyclohexyl groups which may have a substituent.

[0322] As R in the general formula (I) 41 , R 42 , R 43 The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferred.

[0323] As R in the general formula (I) 41 , R 42 , R 43 The alkyl group contained in the alkoxycarbonyl group is preferably the same as the above R 41 , R 42 , R43 The alkyl group in is the same as the alkyl group.

[0324] Preferred substituents in the above-mentioned groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, urea groups, carbamate groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, nitro groups, etc., and preferably, the substituents have 8 or less carbon atoms.

[0325] Ar4 represents an (n+1)-valent aromatic ring group. When n is 1, the divalent aromatic ring group may have a substituent, and preferred examples include arylene groups having 6 to 18 carbon atoms, such as phenylene, tolylene, naphthylene, anthracene, or aromatic ring groups containing heterocycles, such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, etc.

[0326] Specific examples of the (n+1)-valent aromatic ring group when n is an integer of 2 or more include preferably groups obtained by removing (n-1) arbitrary hydrogen atoms from the above-mentioned specific examples of the divalent aromatic ring group.

[0327] The (n+1)-valent aromatic ring group may further have a substituent.

[0328] Examples of the substituents that the alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n+1)-valent aromatic ring group may have include R in the general formula (I): 41 , R 42 , R 43 The alkyl groups listed in, alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, butoxy, and aryl groups such as phenyl.

[0329] As -CONR represented by X4 64 -(R 64 represents a hydrogen atom, an alkyl group) 64 The alkyl group is preferably an alkyl group having 20 or less carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group which may have a substituent, and more preferably an alkyl group having 8 or less carbon atoms.

[0330] X4 is preferably a single bond, -COO-, or -CONH-, and more preferably a single bond or -COO-.

[0331] Preferred examples of the alkylene group in L4 include an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group, which may have a substituent.

[0332] Ar4 is more preferably an aromatic ring group having 6 to 18 carbon atoms which may have a substituent, and is particularly preferably a benzene ring group, a naphthyl ring group, or a biphenylene ring group.

[0333] The repeating unit represented by the general formula (I) preferably has a hydroxystyrene structure. That is, Ar4 is preferably a benzene ring group.

[0334] As the repeating unit having a phenolic hydroxyl group contained in the resin (A), preferably, there can be mentioned a repeating unit represented by the following general formula (p1).

[0335] [Chemical formula 5]

[0336]

[0337] R in the general formula (p1) represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of Rs may be the same or different. In particular, R in the general formula (p1) is preferably a hydrogen atom.

[0338] Ar in the general formula (p1) represents an aromatic ring, for example, an aromatic hydrocarbon ring having 6 to 18 carbon atoms which may have a substituent, such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, a phenanthrene ring, or an aromatic heterocyclic ring containing a heterocyclic ring, such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, a thiazole ring, etc. Among them, a benzene ring is most preferred.

[0339] In the general formula (p1), m represents an integer of 1 to 5, and 1 is preferred.

[0340] Specific examples of the repeating unit having a phenolic hydroxyl group contained in the resin (A) are shown below, but the present invention is not limited thereto.

[0341] [Chemical formula 6]

[0342]

[0343] [Chemical formula 7]

[0344]

[0345] [Chemical formula 8]

[0346]

[0347] The content of the repeating unit having a phenolic hydroxyl group is preferably 0 to 50 mol %, more preferably 0 to 45 mol %, and even more preferably 0 to 40 mol % based on all the repeating units in the resin (A).

[0348] The repeating unit having a group that decomposes by the action of an acid to generate a carboxyl group contained in the resin (A) is a repeating unit having a group in which a hydrogen atom of the carboxyl group is substituted with a group that decomposes by the action of an acid to be released.

[0349] Examples of the group that can be removed by acid include -C(R 36 )(R 37 )(R 38 )、-C(R 36 )(R 37 )(OR 39 )、-C(R 01 )(R 02 )(OR 39 )wait.

[0350] 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.

[0351] 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.

[0352] As the repeating unit having a group that is decomposed by the action of an acid to generate a carboxyl group contained in the resin (A), a repeating unit represented by the following general formula (AI) is preferred.

[0353] [Chemical formula 9]

[0354]

[0355] In the general formula (AI),

[0356] Xa1 represents a hydrogen atom or an alkyl group which may have a substituent.

[0357] T represents a single bond or a divalent linking group.

[0358] Rx1 to Rx3 each independently represent an alkyl group (straight chain or branched) or a cycloalkyl group (monocyclic or polycyclic). In the case where all of Rx1 to Rx3 are alkyl groups (straight chain or branched), it is preferred that at least two of Rx1 to Rx3 are methyl groups.

[0359] Two of Rx1 to Rx3 may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

[0360] 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 Xa1 represents a halogen atom (fluorine atom, etc.), a hydroxyl group or a monovalent organic group, for example, an alkyl group having 5 or less carbon atoms, an acyl group having 5 or less carbon atoms, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. In one embodiment, Xa1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

[0361] Examples of the divalent linking group of 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.

[0362] T is preferably a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH2- group, -(CH2)2 - Group, -(CH2)3-group.

[0363] The alkyl group for Rx1 to Rx3 is preferably an alkyl group having 1 to 4 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, or the like.

[0364] The cycloalkyl group for Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, or an adamantyl group.

[0365] The cycloalkyl group formed by two bonds of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. In particular, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred.

[0366] Regarding the cycloalkyl group formed by two bonds of Rx1 to Rx3, 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.

[0367] The repeating unit represented by the general formula (AI) is preferably, for example, in the embodiment in which Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0368] Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms), and the like, preferably having 8 or less carbon atoms.

[0369] The repeating unit represented by the general formula (AI) is preferably an acid-decomposable tertiary alkyl (meth)acrylate repeating unit (a repeating unit in which Xa1 represents a hydrogen atom or a methyl group and T represents a single bond). More preferably, it is a repeating unit in which Rx1 to Rx3 each independently represent a linear or branched alkyl group, and still more preferably, it is a repeating unit in which Rx1 to Rx3 each independently represent a linear alkyl group.

[0370] Specific examples of the repeating unit having a group that is decomposed by the action of an acid to generate a carboxyl group, which is contained in the resin (A), are shown below, but the present invention is not limited thereto.

[0371] In the specific example, Rx and Xa1 represent hydrogen atoms, CH3, CF3 or CH2OH. Rxa and Rxb represent alkyl groups having 1 to 4 carbon atoms respectively. Z represents a substituent containing a polar group, and when there are multiple substituents, they are independent of each other. p represents 0 or a positive integer. As the substituent containing a polar group represented by Z, for example, a straight-chain or branched alkyl group or cycloalkyl group having a hydroxyl group, a cyano group, an amino group, an alkylamide group or a sulfonamide group can be cited, and an alkyl group having a hydroxyl group is preferred. As a branched alkyl group, an isopropyl group is particularly preferred.

[0372] [Chemical formula 10]

[0373]

[0374] The content of repeating units having a group that decomposes by the action of an acid to generate a carboxyl group is preferably 15 to 90 mol %, more preferably 20 to 90 mol %, further preferably 25 to 80 mol %, and further more preferably 30 to 70 mol % relative to all repeating units in the resin (A).

[0375] The resin (A) preferably further contains a repeating unit having a lactone group.

[0376] As the lactone group, any group can be used as long as it contains a lactone structure, but a group containing a 5- to 7-membered ring lactone structure is preferred, and a 5- to 7-membered ring lactone structure is preferably one in which other ring structures are condensed to form a bicyclic structure or a spirocyclic structure.

[0377] More preferably, the repeating unit contains a group having a lactone structure represented by any one of the following general formulae (LC1-1) to (LC1-16). In addition, the group having a lactone structure may be directly bonded to the main chain. Preferred lactone structures are groups represented by general formulae (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14).

[0378] [Chemical formula 11]

[0379]

[0380] The lactone structure part may have a substituent (Rb2) or may not 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 1 to 8 carbon atoms, carboxyl groups, halogen atoms, hydroxyl groups, cyano groups, acid-decomposable groups, etc. n2 represents an integer of 0 to 4. When n2 is 2 or more, multiple Rb2s may be the same or different, and multiple Rb2s may be bonded to each other to form a ring.

[0381] Examples of the repeating unit containing a group having a lactone structure represented by any one of the general formulae (LC1-1) to (LC1-16) include repeating units represented by the following general formula (AII).

[0382] [Chemical formula 12]

[0383]

[0384] In the general formula (AII), Rb0 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms.

[0385] Preferred substituents that the alkyl group of Rb0 may have include a hydroxyl group and a halogen atom.

[0386] Examples of the halogen atom of Rb0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb0 is preferably a hydrogen atom or a methyl group.

[0387] Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group formed by combining them. Preferably, it is a single bond or a linking group represented by -Ab1-CO2-. Ab1 is a straight chain, a branched alkylene group, a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.

[0388] V represents a group represented by any one of General Formulae (LC1-1) to (LC1-16).

[0389] The repeating unit of the group having a lactone structure generally has optical isomers, but any optical isomer may be used. In addition, one optical isomer may be used alone, or a plurality of optical isomers may be used in combination. When one optical isomer is mainly used, its optical purity (ee) is preferably 90% or more, more preferably 95% or more.

[0390] Specific examples of the repeating unit of the group having a lactone structure are listed below, but the present invention is not limited to these specific examples.

[0391] [Chemical formula 13]

[0392] (Rx H, CH3, CH2OH, CF3)

[0393]

[0394] [Chemical formula 14]

[0395]

[0396] The content of the repeating unit having a lactone group is preferably 1 to 65 mol %, more preferably 1 to 30 mol %, further preferably 5 to 25 mol %, and further more preferably 5 to 20 mol % based on all the repeating units in the resin (A).

[0397] The resin (A) may further include a repeating unit containing an organic group having a polar group, in particular, a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group.

[0398] This improves substrate adhesion and developer affinity.

[0399] As the alicyclic hydrocarbon structure substituted with a polar group, adamantyl, diamantyl, and norbornyl are preferred. As the polar group, a hydroxyl group and a cyano group are preferred.

[0400] Specific examples of the repeating unit having a polar group are listed below, but the present invention is not limited to these specific examples.

[0401] [Chemical formula 15]

[0402]

[0403] When resin (A) contains the following repeating units, the content thereof is preferably 1 to 50 mol%, more preferably 1 to 30 mol%, further preferably 5 to 25 mol%, further more preferably 5 to 20 mol%, relative to all repeating units in resin (A), and the repeating units contain an organic group having a polar group.

[0404] Furthermore, as repeating units other than the above, repeating units having a group (photoacid generating group) that generates an acid by irradiation with actinic rays or radiation may also be included. In this case, it can be considered that the repeating unit having the photoacid generating group is equivalent to the compound (B) that generates an acid by irradiation with actinic rays or radiation described later.

[0405] Examples of such a repeating unit include a repeating unit represented by the following general formula (4).

[0406] [Chemical formula 16]

[0407]

[0408] R 41 represents a hydrogen atom or a methyl group. 41 Represents a single bond or a divalent linking group. 42 W represents a structural site which is decomposed by irradiation with actinic rays or radiation and generates an acid in the side chain.

[0409] Specific examples of the repeating unit represented by the general formula (4) are shown below, but the present invention is not limited thereto.

[0410] [Chemical formula 17]

[0411]

[0412] In addition, examples of the repeating unit represented by the general formula (4) include repeating units described in paragraphs

[0094] to

[0105] of JP-A-2014-041327.

[0413] When the resin (A) contains a repeating unit having a photoacid generating group, the content of the repeating unit having a photoacid generating group is preferably 1 to 40 mol %, more preferably 5 to 35 mol %, and further preferably 5 to 30 mol % relative to all repeating units in the resin (A).

[0414] The resin (A) can be synthesized by a conventional method (e.g., free radical polymerization). For example, as a general synthesis method, there can be listed: a general polymerization method in which a monomer type and an initiator are dissolved in a solvent and then polymerized by heating; a dropwise polymerization method in which a solution of a monomer type and an initiator is dropwise added to a heated solvent over 1 to 10 hours, and the dropwise polymerization method is preferred.

[0415] Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate; amide solvents such as dimethylformamide and dimethylacetamide; solvents that dissolve the actinic ray or radiation-sensitive resin composition such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone described below. It is preferred to use the same solvent as that used in the actinic ray or radiation-sensitive resin composition for polymerization. This can suppress the generation of particles during storage.

[0416] The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available free radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As a free radical initiator, an azo initiator is preferably used, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferably used. As preferred initiators, azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis(2-methylpropionate), etc. can be cited. The initiator is added or added in batches as needed. After the reaction is completed, it is put into a solvent and the desired polymer is recovered by methods such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass.

[0417] The reaction temperature is usually 10°C to 150°C, preferably 30°C to 120°C, more preferably 60°C to 100°C.

[0418] The following common methods can be applied for purification: liquid-liquid extraction method for removing residual monomers or oligomer components by washing with water or combining with appropriate solvents; purification methods in solution state such as ultrafiltration for extracting and removing only components below a specific molecular weight; reprecipitation method for removing residual monomers by dropping a resin solution into a poor solvent to solidify the resin in the poor solvent; purification methods in solid state such as washing the filtered and separated resin slurry with a poor solvent, etc.

[0419] The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and most preferably 5,000 to 15,000, as measured by the GPC method in terms of polystyrene. By setting the weight average molecular weight to 1,000 to 200,000, it is possible to prevent deterioration of heat resistance or dry etching resistance, and to prevent deterioration of developability or deterioration of film forming properties due to increased viscosity.

[0420] Another particularly preferred aspect of the weight average molecular weight of the resin (A) is 3,000 to 9,500 in terms of polystyrene conversion by GPC. By setting the weight average molecular weight to 3,000 to 9,500, resist residue (hereinafter also referred to as "scum") is particularly suppressed, thereby enabling formation of a better pattern.

[0421] The dispersion (molecular weight distribution) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The smaller the dispersion, the better the resolution and resist shape, and the smoother the side wall of the resist pattern, the better the roughness.

[0422] In the actinic ray-sensitive or radiation-sensitive resin composition, the content of the resin (A) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total solid content.

[0423] In the actinic ray-sensitive or radiation-sensitive resin composition, the resin (A) may be used alone or in combination of two or more.

[0424] Furthermore, the resin (A) may contain a repeating unit represented by the following general formula (VI).

[0425] [Chemical formula 18]

[0426]

[0427] In the general formula (VI),

[0428] R 61 , R 62 and R 63 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. 62 It can be bonded with Ar6 to form a ring. In this case, R 62 represents a single bond or an alkylene group.

[0429] X6 represents a single bond, -COO- or -CONR 64 -. R 64 represents a hydrogen atom or an alkyl group.

[0430] L6 represents a single bond or an alkylene group.

[0431] Ar6 represents an (n+1)-valent aromatic ring group, and in the presence of R 62 When they are bonded to form a ring, they represent an (n+2)-valent aromatic ring group.

[0432] When n≥2, Y2 each independently represents a hydrogen atom or a group that is dissociated by the action of an acid, wherein at least one of Y2 represents a group that is dissociated by the action of an acid.

[0433] n represents an integer of 1 to 4.

[0434] As the group Y2 that is dissociated by the action of an acid, a structure represented by the following general formula (VI-A) is more preferable.

[0435] [Chemical formula 19]

[0436]

[0437] Here, L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining an alkylene group and an aryl group.

[0438] M represents a single bond or a divalent linking group.

[0439] Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group.

[0440] At least two of Q, M, and L1 may be bonded to form a ring (preferably a 5-membered ring or a 6-membered ring).

[0441] The repeating unit represented by the general formula (VI) is preferably a repeating unit represented by the following general formula (3).

[0442] [Chemical formula 20]

[0443]

[0444] In general formula (3),

[0445] Ar3 represents an aromatic ring group.

[0446] R3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group or a heteroatom-containing ring group.

[0447] M3 represents a single bond or a divalent linking group.

[0448] Q3 represents an alkyl group, a cycloalkyl group, an aryl group or a heteroatom-containing ring group.

[0449] At least two of Q3, M3 and R3 may be bonded to form a ring.

[0450] The aromatic ring group represented by Ar3 is the same as Ar6 in the above general formula (VI) when n in the above general formula (VI) is 1, and is more preferably a phenylene group or a naphthylene group, and further preferably a phenylene group.

[0451] Specific examples of the repeating unit represented by the general formula (VI) are shown below, but the present invention is not limited thereto.

[0452] [Chemical formula 21]

[0453]

[0454] [Chemical formula 22]

[0455]

[0456] The resin (A) also preferably contains a repeating unit represented by the following general formula (4).

[0457] [Chemical formula 23]

[0458]

[0459] In the general formula (4),

[0460] R 41 , R 42 and R 43 R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. 42 It can be bonded with L4 to form a ring. In this case, R 42 represents an alkylene group.

[0461] L4 represents a single bond or a divalent linking group. 42 When a ring is formed, it represents a trivalent linking group. 44 and R 45 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group or a heteroatom-containing ring group.

[0462] M4 represents a single bond or a divalent linking group.

[0463] Q4 represents an alkyl group, a cycloalkyl group, an aryl group or a heteroatom-containing ring group.

[0464] It can also be Q4, M4 and R 44 At least two of the are bonded to form a ring.

[0465] R 41 , R 42 and R 43 and R in the above general formula (V) 51 , R 52 , R 53 The meanings are the same, and the preferred ranges are also the same.

[0466] L4 has the same meaning as L5 in the above general formula (V), and the preferred range is also the same.

[0467] R 44 and R 45 It has the same meaning as R3 in the above general formula (3), and the preferred range is also the same.

[0468] M4 has the same meaning as M3 in the above general formula (3), and the preferred range is also the same.

[0469] Q4 has the same meaning as Q3 in the above general formula (3), and the preferred range is also the same.

[0470] As Q4, M4 and R 44 The ring formed by bonding at least two of Q3, M3 and R3 can be mentioned, and the preferred range is also the same.

[0471] Specific examples of the repeating unit represented by the general formula (4) are shown below, but the present invention is not limited thereto.

[0472] [Chemical formula 24]

[0473]

[0474] Furthermore, the resin (A) may contain a repeating unit represented by the following general formula (BZ).

[0475] [Chemical formula 25]

[0476]

[0477] In the general formula (BZ), AR represents an aryl group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and AR may be bonded to each other to form a non-aromatic ring.

[0478] R1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.

[0479] Specific examples of the repeating unit represented by the general formula (BZ) are shown below, but the present invention is not limited to these specific examples.

[0480] [Chemical formula 26]

[0481]

[0482] [Chemical formula 27]

[0483]

[0484] The repeating unit having the above-mentioned acid-decomposable group may be used alone or in combination of two or more.

[0485] The content of repeating units having an acid-decomposable group in the resin (A) is preferably 5 mol% to 80 mol% (the total when multiple types are contained) relative to all repeating units in the above-mentioned resin (A), more preferably 5 mol% to 75 mol%, and further preferably 10 mol% to 65 mol%.

[0486] The resin (A) may contain a repeating unit represented by the following general formula (V) or the following general formula (VI).

[0487] [Chemical formula 28]

[0488]

[0489] In the formula,

[0490] R6 and R7 each independently represent a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group or an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms) or a carboxyl group.

[0491] n3 represents an integer from 0 to 6.

[0492] n4 represents an integer from 0 to 4.

[0493] X4 is a methylene group, an oxygen atom or a sulfur atom.

[0494] Specific examples of the repeating unit represented by the general formula (V) or (VI) are shown below, but the present invention is not limited to these specific examples.

[0495] [Chemical formula 29]

[0496]

[0497] Resin (A) may further include repeating units having silicon atoms in the side chain. As repeating units having silicon atoms in the side chain, for example, (meth) acrylate repeating units having silicon atoms, vinyl repeating units having silicon atoms, etc. can be cited. Repeating units having silicon atoms in the side chain are typically repeating units containing groups having silicon atoms in the side chain, and as groups having silicon atoms, for example, trimethylsilyl, triethylsilyl, triphenylsilyl, tricyclohexylsilyl, tri-trimethylsiloxysilyl, tri-trimethylsilylsilyl, methylbistrimethylsilylsilyl, methylbistrimethylsilyloxysilyl, dimethyltrimethylsilylsilyl, dimethyltrimethylsilyloxysilyl, or cyclic or linear polysiloxanes as described below, or cage-type or ladder-type or random silsesquioxane structures, etc. In the formula, R and R1 each independently represent a monovalent substituent. * represents a bond.

[0498] [Chemical formula 30]

[0499]

[0500] Preferred examples of the repeating unit having the above group include a repeating unit derived from an acrylate or methacrylate compound having the above group, or a repeating unit derived from a compound having the above group and a vinyl group.

[0501] The repeating unit having a silicon atom is preferably a repeating unit having a silsesquioxane structure, thereby being able to exhibit very excellent collapse performance when forming an ultra-fine pattern (for example, a line width of less than 50 nm) and a cross-sectional shape with a high aspect ratio (for example, film thickness / line width of 3 or more).

[0502] Examples of the silsesquioxane structure include a cage silsesquioxane structure, a ladder silsesquioxane structure (ladder silsesquioxane structure), and a random silsesquioxane structure. Among them, a cage silsesquioxane structure is preferred.

[0503] Here, the cage silsesquioxane structure refers to a silsesquioxane structure having a cage-like skeleton. The cage silsesquioxane structure may be a complete cage silsesquioxane structure or an incomplete cage silsesquioxane structure, and is preferably a complete cage silsesquioxane structure.

[0504] In addition, the ladder-type silsesquioxane structure refers to a silsesquioxane structure having a ladder-like skeleton.

[0505] The random silsesquioxane structure refers to a silsesquioxane structure having a random skeleton.

[0506] The cage silsesquioxane structure is preferably a siloxane structure represented by the following formula (S).

[0507] [Chemical formula 31]

[0508]

[0509] In the above formula (S), R represents a monovalent organic group. A plurality of Rs may be the same or different.

[0510] The above-mentioned organic group is not particularly limited. Specific examples include hydroxyl, nitro, carboxyl, alkoxy, amino, mercapto, blocked mercapto (for example, mercapto blocked (protected) by acyl), acyl, imide, phosphino, phosphinyl, silane, vinyl, hydrocarbon group which may have heteroatoms, (meth)acrylic acid group-containing group and epoxy group-containing group.

[0511] Examples of the hetero atom of the hydrocarbon group which may have a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom.

[0512] Examples of the hydrocarbon group of the hydrocarbon group which may have a hetero atom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are combined.

[0513] The aliphatic hydrocarbon group may be any of a straight chain, a branched chain, or a cyclic chain. Specific examples of the aliphatic hydrocarbon group include a straight chain or branched alkyl group (especially a carbon number of 1 to 30), a straight chain or branched alkenyl group (especially a carbon number of 2 to 30), a straight chain or branched alkynyl group (especially a carbon number of 2 to 30), and the like.

[0514] Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 18 carbon atoms, such as phenyl, tolyl, xylyl, and naphthyl.

[0515] When the resin (A) contains the repeating unit having a silicon atom in the side chain, the content thereof is preferably 1 to 30 mol %, more preferably 5 to 25 mol %, and even more preferably 5 to 20 mol % based on all the repeating units in the resin (A).

[0516] (B) Compounds that generate acid by actinic rays or radiation (photoacid generators)

[0517] The actinic ray-sensitive or radiation-sensitive resin composition preferably contains a compound that generates an acid by actinic rays or radiation (hereinafter also referred to as a “photoacid generator <PAG: Photo Acid Generator>”).

[0518] The photoacid generator may be in the form of a low molecular weight compound or in the form incorporated into a part of a polymer. Alternatively, the photoacid generator may be used in the form of a low molecular weight compound and in the form incorporated into a part of a polymer.

[0519] When the photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.

[0520] When the photoacid generator is in a form incorporated into a part of the polymer, it may be incorporated into a part of the resin (A) or into a resin different from the resin (A).

[0521] In the present invention, the photoacid generator is preferably in the form of a low molecular weight compound.

[0522] The photoacid generator is not particularly limited as long as it is a known photoacid generator, but is preferably a compound that generates at least one of an organic acid, such as sulfonic acid, bis(alkylsulfonyl)imide, or tris(alkylsulfonyl)methide, upon irradiation with actinic rays or radiation, preferably electron beams or extreme ultraviolet rays.

[0523] More preferably, there can be mentioned compounds represented by the following general formula (ZI), general formula (ZII) and general formula (ZIII).

[0524] [Chemical formula 32]

[0525]

[0526] In the above general formula (ZI),

[0527] R 201 , R 202 and R 203 Each independently represents an organic group.

[0528] As R 201 , R 202 and R203 The number of carbon atoms of the organic group is usually 1-30, preferably 1-20.

[0529] In addition, R 201 ~R 203 Two of them may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. 201 ~R 203 The group formed by bonding two of , for example, an alkylene group (for example, a butylene group and a pentylene group).

[0530] Z - It represents a non-nucleophilic anion (anion with a significantly low ability to cause a nucleophilic reaction).

[0531] Examples of the non-nucleophilic anion include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions, etc.), sulfonimide anions, bis(alkylsulfonyl)imide anions, tris(alkylsulfonyl)methide anions, and the like.

[0532] The aliphatic part in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, and preferably, a linear or branched alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms are mentioned.

[0533] Preferred examples of the aromatic group in the aromatic sulfonate anion and the aromatic carboxylate anion include aryl groups having 6 to 14 carbon atoms, such as phenyl, tolyl, and naphthyl.

[0534] The alkyl group, cycloalkyl group and aryl group listed above may have a substituent. Specific examples thereof include a nitro group, a halogen atom such as a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms), an alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), a cycloalkylaryloxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkoxyalkoxy group (preferably having 5 to 20 carbon atoms), and a cycloalkylalkoxyalkoxy group (preferably having 8 to 20 carbon atoms).

[0535] As for the aryl group and the ring structure possessed by each group, an alkyl group (preferably having 1 to 15 carbon atoms) can be further mentioned as a substituent.

[0536] Preferred examples of the aralkyl group in the aralkylcarboxylate anion include aralkyl groups having 7 to 12 carbon atoms, such as benzyl, phenethyl, naphthylmethyl, naphthylethyl, and naphthylbutyl.

[0537] Examples of the sulfonyl imide anion include a saccharin anion.

[0538] The alkyl group in the bis(alkylsulfonyl)imide anion and the tri(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the substituent of these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkoxysulfonyl group, an aryloxysulfonyl group, a cycloalkylaryloxysulfonyl group, and the like, and preferably a fluorine atom or an alkyl group substituted with a fluorine atom.

[0539] In addition, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure, thereby increasing the acid strength.

[0540] Examples of other non-nucleophilic anions include phosphorus fluoride (e.g., PF6 - ), boron fluoride (e.g., BF4 - ), antimony fluoride (e.g., SbF6 - )wait.

[0541] As the non-nucleophilic anion, preferably, an aliphatic sulfonate anion in which at least the α position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, a bis(alkylsulfonyl)imide anion in which the alkyl group is substituted with a fluorine atom, and a tri(alkylsulfonyl)methide anion in which the alkyl group is substituted with a fluorine atom. As the non-nucleophilic anion, more preferably, a perfluoroaliphatic sulfonate anion (more preferably, a carbon number of 4 to 8) and a benzenesulfonate anion having a fluorine atom are used, and more preferably, a nonafluorobutanesulfonate anion, a perfluorooctanesulfonate anion, a pentafluorobenzenesulfonate anion, and a 3,5-bis(trifluoromethyl)benzenesulfonate anion are used.

[0542] From the viewpoint of acid strength, in order to improve sensitivity, the pKa of the generated acid is preferably -1 or less.

[0543] In addition, as the non-nucleophilic anion, anions represented by the following general formula (AN1) can also be mentioned as a preferred embodiment.

[0544] [Chemical formula 33]

[0545]

[0546] In the formula,

[0547] Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.

[0548] R 1 , R 2 Each independently represents a hydrogen atom, a fluorine atom or an alkyl group, and when there are plural of them, R 1 , R 2 They may be the same or different.

[0549] L represents a divalent linking group, and when a plurality of L exist, they may be the same or different.

[0550] A represents a cyclic organic group.

[0551] x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

[0552] The general formula (AN1) will be described in more detail.

[0553] The alkyl group in the alkyl group substituted with a fluorine atom of Xf preferably has 1 to 10 carbon atoms, and more preferably has 1 to 4 carbon atoms. The alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.

[0554] Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include a fluorine atom, CF3, C2F5, C3F7, C4F9, CH2CF3, CH2CH2CF3, CH2C2F5, CH2CH2C2F5, CH2C3F7, CH2CH2C3F7, CH2C4F9, and CH2CH2C4F9, among which a fluorine atom and CF3 are preferred.

[0555] In particular, it is preferred that both Xf are fluorine atoms.

[0556] R 1 , R 2 The alkyl group may have a substituent (preferably a fluorine atom), and is preferably an alkyl group having 1 to 4 carbon atoms. More preferably, it is a perfluoroalkyl group having 1 to 4 carbon atoms. 1 , R 2 Specific examples of alkyl groups having a substituent include CF3, C2F5, C3F7, C4F9, C5F 11 、C6F 13 、C7F 15 、C8F 17 , CH2CF3, CH2CH2CF3, CH2C2F5, CH2CH2C2F5, CH2C3F7, CH2CH2C3F7, CH2C4F9, CH2CH2C4F9, among which CF3 is preferred.

[0557] As R 1 , R 2 , preferably a fluorine atom or CF3.

[0558] x is preferably 1-10, more preferably 1-5.

[0559] y is preferably 0 to 4, and more preferably 0.

[0560] z is preferably 0-5, more preferably 0-3.

[0561] The divalent linking group of L is not particularly limited, and examples thereof include -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO2-, an alkylene group, a cycloalkylene group, an alkenylene group, or a linking group formed by linking a plurality of these groups, and preferably a linking group having a total carbon number of 12 or less. Among them, -COO-, -OCO-, -CO-, and -O- are preferred, and -COO- and -OCO- are more preferred.

[0562] In the above general formula (ANI), as a combination of partial structures other than A, SO 3- -CF2-CH2-OCO-, SO 3- -CF2-CHF-CH2-OCO-, SO 3- -CF2-C0O-, SO 3- -CF2-CF2-CH2-, SO 3- -CF2-CH(CF3)-OCO- is a preferred combination.

[0563] The cyclic organic group represented by A is not particularly limited as long as it has a cyclic structure, and examples thereof include an alicyclic group, an aryl group, and a heterocyclic group (including not only aromatic groups but also non-aromatic groups).

[0564] The alicyclic group may be monocyclic or polycyclic, preferably a monocyclic cycloalkyl group such as cyclopentyl, cyclohexyl, cyclooctyl, etc.; and a polycyclic cycloalkyl group such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, adamantyl, etc. Among them, from the viewpoint of being able to suppress diffusion in the film during the post-exposure heating process and improve MEEF (mask error enhancement factor), an alicyclic group having a bulky structure with 7 or more carbon atoms such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, adamantyl, etc. is preferred.

[0565] Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.

[0566] Examples of the heterocyclic group include heterocyclic groups derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Among them, heterocyclic groups derived from a furan ring, a thiophene ring, and a pyridine ring are preferred.

[0567] In addition, as the cyclic organic group, a lactone structure can also be mentioned, and as a specific example, the lactone structure represented by the following general formulae (LC1-1) to (LC1-17) can be mentioned.

[0568] [Chemical formula 34]

[0569]

[0570] The above-mentioned cyclic organic group may also have a substituent, and examples of the above-mentioned substituent include an alkyl group (which may be any of linear, branched, and cyclic, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be any of monocyclic, polycyclic, and spirocyclic, and preferably has 3 to 20 carbon atoms), an aryl group (preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a carbamate group, a urea group, a thioether group, a sulfonamide group, a sulfonate group, etc. In addition, the carbon constituting the cyclic organic group (the carbon contributing to the formation of the ring) may be a carbonyl carbon.

[0571] In addition, the above substituent corresponds to Rb2 in the above (LC1-1) to (LC1-17). In addition, in the above (LC1-1) to (LC1-17), n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of Rb2 may be the same or different, and a plurality of Rb2 may be bonded to each other to form a ring.

[0572] In the general formula (ZI), R 201 , R 202 and R 203 The organic group includes aryl, alkyl, cycloalkyl and the like.

[0573] R 201 , R 202 and R 203 In the above, at least one is preferably an aryl group, and more preferably all three are aryl groups. The aryl group may be a phenyl group, a naphthyl group, or a heteroaryl group such as an indole residue or a pyrrole residue. 201 ~R 203The alkyl and cycloalkyl groups preferably include straight-chain alkyl or branched alkyl groups having 1 to 10 carbon atoms and cycloalkyl groups having 3 to 10 carbon atoms. As the alkyl group, more preferably, methyl, ethyl, n-propyl, isopropyl, n-butyl, etc. can be listed. As the cycloalkyl group, more preferably, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc. can be listed. These groups may further have substituents. As the substituents, halogen atoms such as nitro and fluorine atoms, carboxyl, hydroxyl, amino, cyano, alkoxy (preferably carbon atoms 1 to 15), cycloalkyl (preferably carbon atoms 3 to 15), aryl (preferably carbon atoms 6 to 14), alkoxycarbonyl (preferably carbon atoms 2 to 7), acyl (preferably carbon atoms 2 to 12), alkoxycarbonyloxy (preferably carbon atoms 2 to 7), etc. can be listed, but it is not limited to these substituents.

[0574] Next, general formula (ZII) and general formula (ZIII) are described.

[0575] In the general formula (ZII) and the general formula (ZIII), R 204 ~R 207 Each independently represents an aryl group, an alkyl group or a cycloalkyl group.

[0576] As R 204 ~R 207 The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. 204 ~R 207 The aryl group may be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, etc. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

[0577] As R 204 ~R 207 The alkyl group and the cycloalkyl group in the group include preferably linear or branched alkyl groups having 1 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl) and cycloalkyl groups having 3 to 10 carbon atoms (cyclopentyl, cyclohexyl, norbornyl).

[0578] R 204 ~R 207 The aryl group, alkyl group, and cycloalkyl group may have a substituent. 204 ~R 207 The substituents that the aryl group, alkyl group, and cycloalkyl group may have include, for example, an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 15 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, a phenylthio group, and the like.

[0579] In the general formula (iii), Z represents a non-nucleophilic anion. Specifically, it is the same as the compound explained as Z in the general formula (ZI), and the preferred embodiment is also the same.

[0580] Specific examples of general formulae (ZI) to (ZIII) are shown below, but the present invention is not limited thereto.

[0581] [Chemical formula 35]

[0582]

[0583] In the present invention, from the viewpoint of suppressing diffusion of acid generated by exposure to non-exposed areas and improving resolution, the photoacid generator may be a photoacid generator that generates a volume by irradiation with an electron beam or extreme ultraviolet light. A compound of an acid (more preferably a sulfonic acid) of a size greater than or equal to 100 μm, more preferably a compound producing a volume A compound of an acid (more preferably a sulfonic acid) of a size greater than A compound of an acid (more preferably a sulfonic acid) of a size of Among them, from the viewpoint of sensitivity or coating solvent solubility, the above volume is preferably The following is further preferably The above volume values ​​were obtained using "WinMOPAC" manufactured by FUJITSU LIMITED. That is, the chemical structure of the acid involved in each example was first input, and then the structure was used as the initial structure, and the most stable stereo configuration of each acid was determined by molecular force field calculation using the MM3 method, and then molecular orbital calculation using the PM3 method was performed on these most stable stereo configurations, thereby being able to calculate the "accessible volume" of each acid.

[0584] In the present invention, a photoacid generator that generates the following acid by irradiation with actinic rays or radiation is preferred. In addition, the calculated value of volume (unit: ). The calculated value obtained here is the volume value of the acid in which the proton is bonded to the anion part.

[0585] [Chemical formula 36]

[0586]

[0587] [Chemical formula 37]

[0588]

[0589] [Chemical formula 38]

[0590]

[0591] As the photoacid generator, paragraphs

[0368] to

[0377] of Japanese Patent Application Publication No. 2014-41328 and paragraphs

[0240] to

[0262] of Japanese Patent Application Publication No. 2013-228681 can be cited (

[0339] of the corresponding specification of U.S. Patent Application Publication No. 2015 / 004533), and these contents are incorporated into the specification of the present application. In addition, as preferred specific examples, the following compounds can be cited, but are not limited to these specific examples.

[0592] [Chemical formula 39]

[0593]

[0594] [Chemical formula 40]

[0595]

[0596] [Chemical formula 41]

[0597]

[0598] [Chemical formula 42]

[0599]

[0600] The photoacid generator can be used alone or in combination of two or more.

[0601] The content of the photoacid generator in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 0.1 to 50% by mass, more preferably 5 to 50% by mass, and even more preferably 8 to 40% by mass, based on the total solid content of the composition. In particular, in order to achieve both high sensitivity and high resolution during electron beam or extreme ultraviolet exposure, the content of the photoacid generator is preferably high, more preferably 10 to 40% by mass, and most preferably 10 to 35% by mass.

[0602] (C) Solvent

[0603] When preparing the actinic ray-sensitive or radiation-sensitive resin composition by dissolving the above-mentioned components, a solvent may be used. Examples of the solvent that can be used include organic solvents such as alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactates, alkyl alkoxypropionates, cyclic lactones having 4 to 10 carbon atoms, monoketone compounds having 4 to 10 carbon atoms that may contain a ring, alkylene carbonates, alkyl alkoxy acetates, and alkyl pyruvic acids.

[0604] Preferred examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.

[0605] Preferred examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.

[0606] Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate, and butyl lactate.

[0607] Preferred examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.

[0608] Preferred examples of the cyclic lactone having 4 to 10 carbon atoms include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-octanolactone, and α-hydroxy-γ-butyrolactone.

[0609] Preferred examples of the monoketone compound having 4 to 10 carbon atoms and which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2 ...5-methyl-3-heptanone, 2-heptanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2-heptanone, , 6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcycloheptanone.

[0610] Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.

[0611] Preferred examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-2-propyl acetate.

[0612] Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

[0613] Examples of the solvent that can be preferably used include solvents having a boiling point of 130° C. or higher at normal temperature and pressure. Specifically, examples include cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate, and propylene carbonate.

[0614] In the present invention, the above solvents may be used alone or in combination of two or more.

[0615] In the present invention, a mixed solvent obtained by mixing a solvent containing a hydroxyl group in its structure and a solvent not containing a hydroxyl group may be used as the organic solvent.

[0616] Examples of the hydroxyl group-containing solvent include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethyl lactate. Among these, propylene glycol monomethyl ether and ethyl lactate are particularly preferred.

[0617] Examples of the hydroxyl-free solvent include propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N,N-dimethylacetamide, and dimethyl sulfoxide. Among these, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, and 2-heptanone are most preferred.

[0618] The mixing ratio (by mass) of the hydroxyl-containing solvent to the hydroxyl-free solvent is preferably 1 / 99 to 99 / 1, more preferably 10 / 90 to 90 / 10, and still more preferably 20 / 80 to 60 / 40. In terms of coating uniformity, a mixed solvent containing 50 mass % or more of the hydroxyl-free solvent is particularly preferred.

[0619] The solvent is preferably a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.

[0620] As the solvent, for example, the solvents described in paragraphs 0013 to 0029 of JP-A-2014-219664 may be used.

[0621] (D) Basic compounds

[0622] The actinic ray-sensitive or radiation-sensitive resin composition preferably contains a basic compound (D) in order to reduce a change in performance due to the passage of time from exposure to heating.

[0623] Preferred examples of the basic compound (D) include compounds having structures represented by the following formulae (A) to (E).

[0624] [Chemical formula 43]

[0625]

[0626] In the general formula (A) and the general formula (E), R 200 , R 201 and R 202 may be the same or different, and represent a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (preferably having 6 to 20 carbon atoms). Here, R 201 With R 202 They may be bonded to each other to form a ring.

[0627] As for the alkyl group, as the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferred.

[0628] R 203 , R 204 , R 205 and R 206 They may be the same or different and represent an alkyl group having 1 to 20 carbon atoms.

[0629] The alkyl groups in the general formula (A) and the general formula (E) are more preferably unsubstituted.

[0630] Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, and the like. Further preferred compounds include compounds having an imidazole structure, a diazabicyclic structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, or a pyridine structure, alkylamine derivatives having a hydroxyl group and / or an ether bond, and aniline derivatives having a hydroxyl group and / or an ether bond.

[0631] Examples of compounds having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole. Examples of compounds having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undec-7-ene. Examples of compounds having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxides having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tri(tert-butylphenyl)sulfonium hydroxide, bis(tert-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. As a compound having an onium carboxylate structure, a compound having an onium hydroxide structure in which the anion portion is a carboxylate, for example, acetate, adamantane-1-carboxylate, perfluoroalkyl carboxylate, etc. can be cited. As a compound having a trialkylamine structure, tri(n-butyl)amine, tri(n-octyl)amine, etc. can be cited. As a compound having an aniline structure, 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, N,N-dihexylaniline, etc. can be cited. As an alkylamine derivative having a hydroxyl group and / or an ether bond, ethanolamine, diethanolamine, triethanolamine, tri(methoxyethoxyethyl)amine, etc. can be cited. As an aniline derivative having a hydroxyl group and / or an ether bond, N,N-bis(hydroxyethyl)aniline, etc. can be cited.

[0632] Preferred basic compounds further include amine compounds having a phenoxy group and ammonium salt compounds having a phenoxy group.

[0633] The amine compound can be a primary, secondary or tertiary amine compound, and is preferably an amine compound in which at least one alkyl group is bonded to a nitrogen atom. The amine compound is more preferably a tertiary amine compound. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, in addition to the alkyl group, a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 12 carbon atoms) may also be bonded to the nitrogen atom.

[0634] In addition, the amine compound preferably has an oxygen atom in the alkyl chain and forms an oxyalkylene group. The number of oxyalkylene groups in the molecule is 1 or more, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, oxyethylene (-CH2CH2O-) or oxypropylene (-CH(CH3)CH2O- or -CH2CH2CH2O-) is also preferred, and oxyethylene is more preferred.

[0635] The ammonium salt compound can be a primary, secondary, tertiary or quaternary ammonium salt compound, preferably an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom. In the ammonium salt compound, as long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom in addition to an alkyl group.

[0636] The ammonium salt compound preferably has an oxygen atom in the alkyl chain and forms an oxyalkylene group. The number of oxyalkylene groups in the molecule is 1 or more, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, oxyethylene (-CH2CH2O-) or oxypropylene (-CH(CH3)CH2O- or -CH2CH2CH2O-) is preferred, and oxyethylene is more preferred.

[0637] As anions of the ammonium salt compound, halogen atoms, sulfonates, borates, phosphates, etc. can be cited, among which halogen atoms and sulfonates are preferred. As halogen atoms, chlorides, bromides, and iodides are particularly preferred, and as sulfonates, organic sulfonates having 1 to 20 carbon atoms are particularly preferred. As organic sulfonates, alkyl sulfonates and aryl sulfonates having 1 to 20 carbon atoms can be cited. The alkyl group of the alkyl sulfonate can also have a substituent, and as the substituent, for example, fluorine, chlorine, bromine, alkoxy, acyl, aryl, etc. can be cited. As alkyl sulfonates, specifically, methane sulfonates, ethane sulfonates, butane sulfonates, hexane sulfonates, octane sulfonates, benzyl sulfonates, trifluoromethane sulfonates, pentafluoroethane sulfonates, nonafluorobutane sulfonates, etc. can be cited. As the aryl group of the aryl sulfonate, benzene rings, naphthalene rings, and anthracene rings can be cited. Benzene rings, naphthalene rings, and anthracene rings can also have substituents, and as substituents, linear or branched alkyl groups having 1 to 6 carbon atoms and cycloalkyl groups having 3 to 6 carbon atoms are preferred. Specific examples of the straight chain alkyl group or branched alkyl group and the cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, and cyclohexyl groups. Other substituents include alkoxy groups having 1 to 6 carbon atoms, halogen atoms, cyano groups, nitro groups, acyl groups, and acyloxy groups.

[0638] The so-called amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group refer to a phenoxy group at the end opposite to the nitrogen atom of the alkyl group of the amine compound or the ammonium salt compound. The phenoxy group may also have a substituent. As the substituent of the phenoxy group, for example, an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylate group, a sulfonate group, an aryl group, an aralkyl group, an acyloxy group, an aryloxy group, etc. can be listed. The substitution position of the substituent may be any one of the 2nd to 6th positions. The number of substituents may be any one within the range of 1 to 5.

[0639] It is preferred that there is at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups in the molecule is 1 or more, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, oxyethylene (-CH2CH2O-) or oxypropylene (-CH(CH3)CH2O- or -CH2CH2CH2O-) is also preferred, and oxyethylene is more preferred.

[0640] The amine compound having a phenoxy group can be obtained by heating and reacting a primary amine or secondary amine having a phenoxy group with a halogenated alkyl ether, adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, or tetraalkylammonium, and extracting with an organic solvent such as ethyl acetate or chloroform. Alternatively, the amine compound can be obtained by heating and reacting a primary amine or secondary amine with a halogenated alkyl ether having a phenoxy group at the end, adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, or tetraalkylammonium, and extracting with an organic solvent such as ethyl acetate or chloroform.

[0641] (Compounds (PA) having proton accepting functional groups and decomposing by irradiation with actinic rays or radiation to produce compounds whose proton accepting properties are reduced or eliminated or whose proton accepting properties are changed to acidic properties)

[0642] The composition involved in the present invention may further contain the following compound (hereinafter also referred to as compound (PA)) as a basic compound, which has a proton accepting functional group and is decomposed by irradiation with actinic rays or radiation to produce a compound whose proton accepting property is reduced, disappears, or changes from proton accepting property to acidic.

[0643] The so-called proton accepting functional group refers to a group that can electrostatically interact with a proton or a functional group having an electron, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group having a nitrogen atom with an unshared electron pair that does not contribute to π conjugation. The so-called nitrogen atom having an unshared electron pair that does not contribute to π conjugation refers to, for example, a nitrogen atom having a partial structure represented by the following general formula.

[0644] [Chemical formula 44]

[0645]

[0646] Preferred partial structures of the proton accepting functional group include crown ethers, azacrown ethers, primary and tertiary amines, pyridine, imidazole, and pyrazine structures.

[0647] The compound (PA) is decomposed by irradiation with actinic rays or radiation to generate a compound whose proton accepting property is reduced, disappears, or changes from proton accepting property to acidic property. Here, the reduction, disappearance, or change from proton accepting property to acidic property refers to the change of proton accepting property caused by the addition of protons to the proton accepting functional group, and specifically refers to the decrease in the equilibrium constant in the chemical equilibrium when a proton adduct is generated by a compound (PA) having a proton accepting functional group and a proton.

[0648] Specific examples of compound (PA) include the following compounds. Specific examples of compound (PA) include compounds described in paragraphs 0421 to 0428 of Japanese Patent Application Laid-Open No. 2014-41328 and paragraphs 0108 to 0116 of Japanese Patent Application Laid-Open No. 2014-134686, and the contents thereof are incorporated herein.

[0649] [Chemical formula 45]

[0650]

[0651] [Chemical formula 46]

[0652]

[0653] [Chemical formula 47]

[0654]

[0655] These basic compounds can be used alone or in combination of two or more.

[0656] The amount of the basic compound used is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the actinic ray-sensitive or radiation-sensitive composition.

[0657] The ratio of the photoacid generator to the basic compound in the composition is preferably photoacid generator / basic compound (molar ratio) = 2.5 to 300. That is, from the perspective of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the perspective of suppressing the decrease in resolution due to the roughness of the resist pattern after exposure until the heat treatment, the molar ratio is preferably 300 or less. The photoacid generator / basic compound (molar ratio) is more preferably 5.0 to 200, and further preferably 7.0 to 150.

[0658] As the basic compound, for example, compounds described in 0140 to 0144 of JP-A-2013-11833 (amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc.) can be used.

[0659] (A') Hydrophobic resin

[0660] The actinic ray-sensitive or radiation-sensitive resin composition may have a hydrophobic resin (A') different from the above-mentioned resin (A).

[0661] The hydrophobic resin is preferably designed so as to be present preferentially on the surface of the resist film, but unlike a surfactant, it does not necessarily need to have a hydrophilic group in the molecule and may not contribute to uniform mixing of polar / nonpolar substances.

[0662] Examples of the effects of adding a hydrophobic resin include control of the static contact angle and dynamic contact angle of the resist film surface with respect to water and suppression of outgassing.

[0663] From the viewpoint of being present in the film surface, the hydrophobic resin preferably has one or more of "fluorine atom", "silicon atom" and "CH3 partial structure contained in the side chain of the resin", and more preferably has two or more. In addition, the hydrophobic resin preferably contains a hydrocarbon group with a carbon number of 5 or more. These groups may be included in the main chain of the resin or substituted in the side chain.

[0664] When the hydrophobic resin contains fluorine atoms and / or silicon atoms, the fluorine atoms and / or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin or in the side chain.

[0665] When the hydrophobic resin contains a fluorine atom, it is preferably a resin containing an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.

[0666] The alkyl group having fluorine atoms (preferably having 1 to 10 carbon atoms, more preferably having 1 to 4 carbon atoms) is a straight-chain or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.

[0667] The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.

[0668] Examples of the aryl group having a fluorine atom include an aryl group such as a phenyl group and a naphthyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the aryl group may further have a substituent other than a fluorine atom.

[0669] Examples of the repeating unit having a fluorine atom or a silicon atom include those listed in paragraph 0519 of US 2012 / 0251948 A1.

[0670] Furthermore, as described above, the hydrophobic resin also preferably contains a CH3 partial structure in the side chain portion.

[0671] Here, the CH3 partial structure in the side chain part of the hydrophobic resin includes a CH3 partial structure of an ethyl group, a propyl group, or the like.

[0672] On the other hand, the methyl group directly bonded to the main chain of the hydrophobic resin (for example, the α-methyl group of the repeating unit having a methacrylic acid structure) contributes little to the hydrophobic resin being preferentially present on the surface due to the influence of the main chain, and is therefore not included in the CH3 partial structure in the present invention.

[0673] Regarding the hydrophobic resin, reference can be made to the descriptions of

[0348] to

[0415] of JP-A-2014-010245, and these contents are incorporated into the specification of the present application.

[0674] Furthermore, as the hydrophobic resin, hydrophobic resins described in Japanese Patent Application Laid-Open Nos. 2011-248019, 2010-175859, and 2012-032544 can also be preferably used.

[0675] (E) Surfactant

[0676] The actinic ray-sensitive or radiation-sensitive resin composition may further contain a surfactant (E). By containing a surfactant, when using an exposure light source with a wavelength of 250 nm or less, especially 220 nm or less, a pattern with good sensitivity and resolution, adhesion and fewer development defects can be formed.

[0677] As the surfactant, it is particularly preferable to use a fluorine-based and / or silicon-based surfactant.

[0678] Examples of the fluorine-based and / or silicon-based surfactants include surfactants described in

[0276] of US Patent Application Publication No. 2008 / 0248425. In addition, Eftop EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Fluorad FC430, 431 or 4430 (manufactured by Sumitomo 3M Limited); MEGAFACE F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by ASAHI GLASS CO., LTD.); Troysol S-366 (manufactured by Troy Chemical Industries Inc.); GF-300 or GF-150 (manufactured by TOAGOSEI CO., LTD.), Surflon S-393 (manufactured by AGC SEIMI CHEMICAL CO., LTD.); Eftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (manufactured by JEMCO INC.); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA Solutions Inc.); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos Corporation). In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

[0679] In addition to the known surfactants as shown above, the surfactant can also be synthesized using a fluoroaliphatic compound produced by a telomerization method (also called a telomer method) or an oligomerization method (also called an oligomer method). Specifically, a polymer having a fluoroaliphatic group derived from the fluoroaliphatic compound can also be used as a surfactant. The fluoroaliphatic compound can be synthesized, for example, by the method described in Japanese Patent Application Publication No. 2002-90991.

[0680] In addition, surfactants other than fluorine-based and / or silicon-based surfactants described in

[0280] of the specification of US Patent Application Publication No. 2008 / 0248425 may also be used.

[0681] These surfactants may be used alone or in combination of two or more.

[0682] When the actinic ray-sensitive or radiation-sensitive resin composition contains a surfactant, the content thereof is preferably 0 to 2 mass %, more preferably 0.0001 to 2 mass %, and further preferably 0.0005 to 1 mass % based on the total solid content of the composition.

[0683] (F) Other additives

[0684] The actinic ray or radiation-sensitive resin composition may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber and / or a compound that promotes solubility in a developer (eg, a phenol compound having a molecular weight of 1000 or less or an alicyclic or aliphatic compound containing a carboxyl group).

[0685] The actinic ray-sensitive or radiation-sensitive resin composition may further contain a dissolution-inhibiting compound.

[0686] Here, the “dissolution inhibiting compound” refers to a compound having a molecular weight of 3,000 or less that is decomposed by the action of an acid and has a reduced solubility in an organic developer.

[0687] <[Upper film (top coating)]

[0688] In the pattern forming method of the present invention, an upper layer film (top coat film) may be formed on the upper layer of the resist film.

[0689] It is preferable that the upper layer film is not mixed with the resist film and can be evenly coated on the upper layer of the resist film.

[0690] There is no particular limitation on the upper film, and the upper film can be formed by a conventionally known method, for example, the upper film can be formed according to the description of paragraphs 0072 to 0082 of Japanese Patent Publication No. 2014-059543. In addition to the polymer described in paragraph 0072 of Japanese Patent Publication No. 2014-059543, a hydrophobic resin or the like can also be used as the material for forming the upper film. For example, the hydrophobic resin (A') described above can be used as the hydrophobic resin.

[0691] In the development step, when a developer containing an organic solvent is used, it is preferred to form an upper layer film containing a basic compound as described in JP-A-2013-61648 on the resist film. Specific examples of the basic compound that can be contained in the upper layer film include the basic compound (E).

[0692] Furthermore, the upper layer film preferably contains a compound having at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

[0693] Furthermore, the upper layer film may contain a photoacid generator. As the photoacid generator, the same photoacid generator as that contained in the actinic ray-sensitive or radiation-sensitive composition (for example, the above-mentioned photoacid generator (B)) can be used.

[0694] Hereinafter, resins preferably used for the upper layer film (top coating film) will be described.

[0695] (resin)

[0696] The upper film-forming composition preferably contains a resin. The resin that can be contained in the upper film-forming composition is not particularly limited, and the same resin as the hydrophobic resin that can be contained in the actinic ray-sensitive or radiation-sensitive composition (for example, the above-mentioned hydrophobic resin (A')) can be used.

[0697] Regarding the hydrophobic resin, reference may be made to paragraphs 0017 to 0023 of Japanese Patent Application Publication No. 2013-61647 (paragraphs 0017 to 0023 of the corresponding U.S. Patent Publication No. 2013 / 244438) and paragraphs 0016 to 0165 of Japanese Patent Application Publication No. 2014-56194, the contents of which are incorporated into the present specification.

[0698] In this specification, the composition for forming the upper film preferably contains a resin containing a repeating unit having an aromatic ring. By containing a repeating unit having an aromatic ring, the generation efficiency of secondary electrons and the acid generation efficiency of compounds that generate acids by actinic rays or radiation are increased, especially during electron beam or EUV exposure, and the effects of high sensitivity and high resolution can be expected during pattern formation.

[0699] The weight average molecular weight of the resin is preferably 3000 to 100000, more preferably 3000 to 30000, and most preferably 5000 to 20000. The amount of the resin in the composition for forming an upper layer film is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, more preferably 70 to 99.7% by mass, and even more preferably 80 to 99.5% by mass in the total solid content.

[0700] When the upper layer film-forming composition (top coating composition) contains a plurality of resins, it preferably contains at least one resin (XA) having a fluorine atom and / or a silicon atom.

[0701] Regarding the preferred range of the content of fluorine atoms and silicon atoms contained in the resin (XA), the repeating unit containing fluorine atoms and / or silicon atoms in the resin (XA) is preferably 10 to 100% by mass, preferably 10 to 99% by mole, and more preferably 20 to 80% by mole.

[0702] In addition, the composition for forming the upper film more preferably contains at least one of the resins (XA) having fluorine atoms and / or silicon atoms, and a resin (XB) having a lower content of fluorine atoms and / or silicon atoms than the resin (XA). Thus, when the upper film is formed, the resin (XA) is preferentially present on the surface of the upper film, thereby improving the performance such as the developing characteristics and the ability to follow the immersion liquid.

[0703] Based on the total solid content contained in the composition for forming a layer film, the content of the resin (XA) is preferably 0.01 to 30% by mass, more preferably 0.1 to 10% by mass, further preferably 0.1 to 8% by mass, and particularly preferably 0.1 to 5% by mass. Based on the total solid content contained in the composition for forming a layer film, the content of the resin (XB) is preferably 50.0 to 99.9% by mass, more preferably 60 to 99.9% by mass, further preferably 70 to 99.9% by mass, and particularly preferably 80 to 99.9% by mass.

[0704] The resin (XB) is preferably in a form that does not substantially contain fluorine atoms and silicon atoms. In this case, specifically, the total content of repeating units having fluorine atoms and repeating units having silicon atoms is preferably 0 to 20 mol%, more preferably 0 to 10 mol%, further preferably 0 to 5 mol%, particularly preferably 0 to 3 mol%, and ideally 0 mol%, that is, it contains no fluorine atoms and silicon atoms.

[0705] <Preparation method of upper film-forming composition (butyl coating composition)>

[0706] The composition for forming the upper film preferably dissolves each component in a solvent and filters it. As a filter, it is preferably a filter made of polytetrafluoroethylene, polyethylene, or nylon with a pore size of less than 0.1 μm, more preferably less than 0.05 μm, and more preferably less than 0.03 μm. In addition, a variety of filters can be connected in series or in parallel and used. In addition, the composition can also be filtered multiple times, and the process of filtering multiple times can be a circulating filtration process. Furthermore, the composition can also be degassed before and after filtering by the filter. The composition for forming the upper film preferably does not include impurities such as metals. As the content of the metal component contained in these materials, it is preferably less than 10 ppm, more preferably less than 5 ppm, more preferably less than 1 ppm, and particularly preferably substantially not included (below the detection limit of the measuring device).

[0707] In the above-mentioned <exposure step>, when the exposure is set as immersion exposure, the upper film also functions as a layer arranged between the actinic ray or radiation-sensitive film and the immersion liquid so that the actinic ray or radiation-sensitive film does not directly contact the immersion liquid. In this case, the properties preferably possessed by the upper film (composition for forming the upper film) are coating suitability for the actinic ray or radiation-sensitive film, transparency to radiation, especially 193nm, and poor solubility in the immersion liquid (preferably water). In addition, the upper film is preferably not mixed with the actinic ray or radiation-sensitive film, and can be further uniformly coated on the surface of the actinic ray or radiation-sensitive film.

[0708] In addition, in order to uniformly apply the composition for forming an upper layer film on the surface of the actinic ray-sensitive or radiation-sensitive film without dissolving the actinic ray-sensitive or radiation-sensitive film, the composition for forming an upper layer film preferably contains a solvent that does not dissolve the actinic ray-sensitive or radiation-sensitive film. As the solvent that does not dissolve the actinic ray-sensitive or radiation-sensitive film, it is further preferred to use a solvent having a component different from that of a developer containing an organic solvent (organic developer).

[0709] The coating method of the upper layer film-forming composition is not particularly limited, and conventionally known methods such as spin coating, spraying, roll coating, and dipping can be used.

[0710] The thickness of the upper layer film is not particularly limited, but is usually 5 nm to 300 nm, preferably 10 nm to 300 nm, more preferably 20 nm to 200 nm, and further preferably 30 nm to 100 nm from the viewpoint of transparency to an exposure light source.

[0711] After the upper layer film is formed, the substrate is heated (PB) as necessary.

[0712] From the viewpoint of resolution, the refractive index of the upper layer film is preferably close to the refractive index of the actinic ray-sensitive or radiation-sensitive film.

[0713] The upper film is preferably insoluble in the immersion liquid, more preferably insoluble in water.

[0714] The receding contact angle of the upper film is preferably 50 to 100 degrees, more preferably 80 to 100 degrees, from the viewpoint of immersion liquid followability.

[0715] In liquid immersion exposure, the immersion liquid needs to move on the chip to follow the action of the exposure head scanning the chip at high speed to form an exposure pattern. Therefore, the contact angle of the immersion liquid in the dynamic state with respect to the photosensitive radiation or radiation-sensitive film becomes important. In order to obtain better anti-etching agent performance, it is preferred to have a receding contact angle within the above range.

[0716] When peeling the upper film, an organic developer may be used, or a stripping solution may be used separately. As the stripping solution, a solvent having low permeability to the photosensitive ray or radiation-sensitive film is preferred. In terms of being able to simultaneously perform the stripping of the upper film and the development of the photosensitive ray or radiation-sensitive film, the upper film is preferably capable of being stripped by an organic developer. As the organic developer used for stripping, there is no particular limitation as long as it can dissolve and remove the low-exposure portion of the photosensitive ray or radiation-sensitive film.

[0717] From the viewpoint of peeling with an organic developer, the dissolution rate of the upper layer film with respect to the organic developer is preferably 1 to 300 nm / sec, more preferably 10 to 100 nm / sec.

[0718] Here, the dissolution rate of the upper layer film in the organic developer refers to the film thickness reduction rate when the upper layer film is exposed to the developer after film formation, and in the present invention, it is the rate when immersed in butyl acetate at 23°C.

[0719] By setting the dissolution rate of the upper film to the organic developer to be 1 nm / sec or more, preferably 10 nm / sec or more, there is an effect of reducing the occurrence of development defects after developing the actinic ray-sensitive or radiation-sensitive film. In addition, by setting it to 300 nm / sec or less, preferably 100 nm / sec, there is an effect of further improving the line edge roughness of the pattern after developing the actinic ray-sensitive or radiation-sensitive film due to the reduced influence of exposure unevenness during immersion exposure.

[0720] The upper layer film can also be removed using other known developing solutions, for example, alkaline aqueous solutions, etc. As the alkaline aqueous solution that can be used, specifically, an aqueous solution of tetramethylammonium hydroxide can be mentioned.

[0721] In addition, the present invention also relates to a method for manufacturing an electronic device including the pattern forming method of the present invention.

[0722] The electronic device manufactured by the method for manufacturing an electronic device of the present invention is preferably mounted in electric and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, communication equipment, etc.).

[0723] Example

[0724] Hereinafter, the present invention will be described in detail by way of examples, but the content of the present invention is not limited thereto. In addition, "%", "ppb" and "ppt" are based on mass unless otherwise specified.

[0725] <<Preparation of Processing Liquid for Semiconductor Manufacturing>>

[0726] Hereinafter, synthesis examples of various treatment liquids will be described, but the treatment liquids are not limited to the following synthesis examples, and can be synthesized using known methods.

[0727] [Examples 1 to 46, Comparative Examples 1 to 2]

[0728] <Purification of raw materials, etc.>

[0729] The raw materials and catalysts used in the following examples are high purity grades with a purity of 99% by mass or more, and are further purified in advance by distillation, ion exchange, filtration, etc. In addition, the catalyst used in the esterification reaction shown below is sulfuric acid. The sulfuric acid used as the catalyst is sulfuric acid with a purity of 98% by mass or more, and dilute sulfuric acid can also be supplied and used while being dehydrated to a predetermined concentration range.

[0730] The ultrapure water used in the examples was purified by the method described in Japanese Patent Application Laid-Open No. 2007-254168 and confirmed by the SP-ICP-MS method described below that the content of each element of Na, Ca and Fe was less than 10 ppt by mass relative to the total mass of each treatment liquid.

[0731] The preparation, filling, storage, and analysis of the treatment liquid were all performed in a clean room satisfying a level lower than ISO Class 2. In addition, the container used in the examples was used after being cleaned in advance with the treatment liquid of the present invention.

[0732] <Synthesis example 1>

[0733] Synthesis of a treatment solution containing butyl acetate (treatment solution 1A)

[0734] (Process 1)

[0735] Acetic acid and n-butanol were preliminarily reacted in a continuous tank reactor in the presence of sulfuric acid as a catalyst. Then, the reaction solution 1a obtained was reacted in a continuous reactive distillation column while removing water produced as a by-product as an azeotropic mixture of butyl acetate / n-butanol / water from the top of the distillation column to the outside of the system, thereby obtaining a crude liquid containing butyl acetate (hereinafter referred to as "crude butyl acetate liquid") 1b.

[0736] (Process 2)

[0737] The sulfuric acid component of the crude butyl acetate liquid 1b obtained in step 1 was neutralized with alkali, and then washed with water and the water was removed to obtain a crude butyl acetate liquid 1c.

[0738] (Process 3)

[0739] The crude butyl acetate liquid 1c obtained in step 2 is neutralized and washed with water, and most of the water and sulfuric acid are separated by a decanter. Next, the crude butyl acetate liquid 1d containing butyl acetate, n-butanol, water, sulfuric acid and a small amount of by-products is supplied to a distillation column for the purpose of removing low-boiling substances such as n-butanol and water as impurities. Then, distillation is repeated several times to obtain a treated liquid containing butyl acetate as a target product (treated liquid 1A).

[0740] The compounds (B) contained in the obtained butyl acetate-containing treatment liquid (treatment liquid 1A) were the following compounds. The contents of these compounds in the treatment liquid all satisfied the requirement (b) (see Table 2).

[0741] [Chemical formula 48]

[0742]

[0743] Other treatment solutions containing butyl acetate (treatment solutions 1B to 1Q) were synthesized in the same manner as in Synthesis Example 1. The compound (B) contained in each of the treatment solutions obtained was the same as that in treatment solution 1A, and the content of the compound (B) in each treatment solution satisfied requirement (b) (see Table 2).

[0744] <Synthesis example 2>

[0745] Synthesis of a treatment solution containing 1-hexanol (treatment solution 2A)

[0746] (Raw materials, etc.)

[0747] 1-Hexanol is synthesized by the following two-step reaction formula.

[0748] Al(C2H5)3+6C2H4→Al(C6H 13 )3

[0749] Al(C6H 13 )3+3 / 2O2+3H2O→3HOC6H 13 +Al(OH)3

[0750] (Process 1)

[0751] The polymerized Al(C6H 15 )3. Next, the A1(C6H 15 )3 as a catalyst and in the presence of oxygen and water, 1-hexanol was synthesized according to a known method. Here, a crude liquid containing 1-hexanol (hereinafter referred to as "1-hexanol crude liquid") 2a was obtained by heating at 40°C for 10 hours. Al was removed as aluminum hydroxide.

[0752] (Process 2)

[0753] Since the 1-hexanol crude liquid 2a obtained in step 1 contained a precipitate of Al(OH) 3 , Al(OH) 3 was removed by filtration to obtain a 1-hexanol crude liquid 2b.

[0754] (Process 3)

[0755] The crude 1-hexanol liquid 2b obtained in step 2 is supplied to a distillation column for the purpose of removing by-products such as substituted isomers and higher alcohols. Then, distillation is repeated several times to obtain a treated liquid (treated liquid 2A) containing 1-hexanol as a target product.

[0756] The compounds (B) contained in the obtained treatment liquid containing 1-hexanol (treatment liquid 2A) are the following compounds. The contents of these compounds in the treatment liquid all satisfy the requirement (b) (see Table 2).

[0757] [Chemical formula 49]

[0758]

[0759] <Synthesis example 3>

[0760] Synthesis of a treatment solution containing 4-methyl-2-pentanol (treatment solution 3A)

[0761] (Process 1)

[0762] With respect to cis-4-methyl-2-pentene, 4-methyl-2-pentanol was synthesized according to a known method in the presence of Ipc2BH (diisopinocampheylborane) as a catalyst. Here, a heating treatment was performed at 80°C for 4 hours, and a crude liquid containing 4-methyl-2-pentanol (hereinafter referred to as "4-methyl-2-pentanol crude liquid") 3a was obtained through an intermediate formed by boron bonding between cis-4-methyl-2-pentene and Ipc2BH.

[0763] (Process 2)

[0764] The crude 4-methyl-2-pentanol liquid 3a obtained in step 1 contains unreacted cis-4-methyl-2-pentene and substituted isomers as impurities.

[0765] The crude 4-methyl-2-pentanol liquid 3a was supplied to a distillation column for the purpose of purification. The distillation was repeated several times to obtain a treated liquid (treated liquid 3A) containing 4-methyl-2-pentanol as a target product.

[0766] The compounds (B) contained in the obtained treatment liquid containing 4-methyl-2-pentanol (treatment liquid 3A) are the following compounds. The contents of these compounds in the treatment liquid all satisfy the requirement (b) (see Table 2).

[0767] [Chemical formula 50]

[0768]

[0769] Other treatment liquids containing 4-methyl-2-pentanol (treatment liquids 3B to 3G) were synthesized in the same manner as in Synthesis Example 3. The compound (B) contained in each of the obtained treatment liquids was the same as that in treatment liquid 1A, and the content of any compound (B) in the treatment liquid satisfied requirement (b) (see Table 2).

[0770] <Synthesis example 4>

[0771] Synthesis of a treatment liquid (treatment liquid 4A) containing PGMEA (propylene glycol monomethyl ether acetate)

[0772] (Process 1)

[0773] PGMEA was synthesized by a known method using propylene oxide, methanol, and acetic acid in the presence of sulfuric acid as a catalyst (two-stage synthesis). Here, a crude liquid containing PGMEA (hereinafter referred to as "PGMEA crude liquid") 4a was obtained by heating at 80°C for 8 hours.

[0774] (Process 2)

[0775] The PGMEA crude liquid 4a obtained in step 1 contains unreacted propylene oxide, methanol, acetic acid, and substituted isomers as impurities.

[0776] The crude PGMEA liquid 4a was supplied to a distillation column for the purpose of purification. The distillation was repeated several times to obtain a treated liquid (treated liquid 4A) containing PGMEA as a target product.

[0777] The compounds (B) contained in the obtained PGMEA-containing treatment liquid (treatment liquid 4A) were the following compounds. The contents of these compounds in the treatment liquid all satisfied the requirement (b) (see Table 2).

[0778] [Chemical formula 51]

[0779]

[0780] Other PGMEA-containing treatment liquids (treatment liquids 4B to 4G) were synthesized in the same manner as in Synthesis Example 4. The compound (B) contained in each of the obtained treatment liquids was the same as that in treatment liquid 4A, and the content of any compound (B) in the treatment liquid satisfied requirement (b) (see Table 2).

[0781] <Synthesis example 5>

[0782] Synthesis of a treatment liquid containing IPA (isopropyl alcohol) (treatment liquid 5A)

[0783] (Process 1)

[0784] Acetone reduction reaction was carried out according to a known method using acetone and hydrogen in the presence of copper oxide-zinc oxide-aluminum oxide as a catalyst. Here, a heating treatment was carried out at 100° C. for 4 hours to obtain a crude liquid containing IPA (hereinafter referred to as “IPA crude liquid”) 5a.

[0785] (Process 2)

[0786] The crude IPA liquid 5a contains unreacted acetone, substituted isomers as impurities, and a catalyst. The crude IPA liquid 5a is supplied to a distillation tower for purification. The distillation is repeated several times to obtain a treatment liquid (treatment liquid 5A) containing IPA as a target product.

[0787] The compounds (B) contained in the obtained IPA-containing treatment liquid (treatment liquid 5A) are the following compounds. The content ratios of these compounds in the treatment liquid all satisfy the requirement (b) (see Table 2).

[0788] [Chemical formula 52]

[0789]

[0790] Other IPA-containing treatment liquids (treatment liquids 5B to 5E) were synthesized in the same manner as in Synthesis Example 5. The compound (B) contained in each of the obtained treatment liquids was the same as that in treatment liquid 5A, and the content of any compound (B) in the treatment liquid satisfied requirement (b) (see Table 2).

[0791] <Synthesis example 6>

[0792] Synthesis of a treatment solution containing ethyl lactate (EL) (treatment solution 6A)

[0793] (Process 1)

[0794] A crude liquid containing ethyl lactate (hereinafter referred to as "crude ethyl lactate liquid") 6a was obtained by the esterification method described in Japanese Patent Application Laid-Open No. 62-26249 using lactic acid and ethanol.

[0795] (Process 2)

[0796] The crude ethyl lactate liquid 6a obtained in step 1 contains water produced as a by-product or pure and unreacted raw material ethanol.

[0797] The obtained crude ethyl lactate liquid 6a was supplied to a distillation column for the purpose of purification, and then the distillation was repeated several times to obtain a treated liquid containing ethyl lactate (treated liquid 6A).

[0798] The compounds (B) contained in the obtained ethyl lactate-containing treatment liquid (treatment liquid 6A) were the following compounds. The contents of these compounds in the treatment liquid all satisfied the requirement (b) (see Table 2).

[0799] [Chemical formula 53]

[0800]

[0801] Other treatment solutions containing ethyl lactate (treatment solutions 6B to 6E) were synthesized in the same manner as in Synthesis Example 6. The compound (B) contained in each of the treatment solutions obtained was the same as that in treatment solution 6A, and the content of any compound (B) in the treatment solution satisfied requirement (b) (see Table 2).

[0802] <Synthesis Example 7>

[0803] Synthesis of a treatment liquid containing cyclohexanone (treatment liquid 7A)

[0804] (Process 1)

[0805] By the method described in Japanese Patent Application Laid-Open No. 2007-63209, monochlorobenzene and hydrogen chloride were obtained from benzene and chlorine. Then, phenol and hydrogen chloride were obtained from monochlorobenzene and water. Then, a crude liquid containing cyclohexanone (hereinafter referred to as "cyclohexanone crude liquid") 7a was obtained from phenol and hydrogen.

[0806] (Process 2)

[0807] In step 1, the cyclohexanone crude liquid 7a obtained from the reaction tower contains unreacted benzene, monochlorobenzene, phenol, and the like.

[0808] The obtained cyclohexanone crude liquid 7a was supplied to a distillation column for the purpose of purification. Then, distillation was repeated several times to obtain a treated liquid containing cyclohexanone (treated liquid 7A).

[0809] The compounds (B) contained in the obtained cyclohexanone-containing treatment liquid (treatment liquid 7A) are the following compounds. The content ratios of these compounds in the treatment liquid all satisfy the requirement (b) (see Table 2).

[0810] [Chemical formula 54]

[0811]

[0812] Another treatment liquid containing cyclohexanone (treatment liquid 7E) was synthesized by the same method as in Synthesis Example 7. In addition, for treatment liquids 7B to 7D and treatment liquids 7F to 7G, the crude liquid 7a was purified by the method described below. The compound (B) contained in each of the obtained treatment liquids was the same as that in treatment liquid 7A, and the content of any compound (B) in the treatment liquid satisfied requirement (b) (see Table 2).

[0813] <Synthesis example 8>

[0814] Synthesis of a treatment liquid containing PGME (propylene glycol monomethyl ether) (treatment liquid 8A)

[0815] (Process 1)

[0816] By reacting methanol and propylene oxide at 90 to 110° C. according to the method described in Japanese Patent Application Laid-Open No. 2008-208035, a crude liquid containing PGME (hereinafter referred to as “PGME crude liquid”) 8a was obtained.

[0817] (Process 2)

[0818] In step 1, the PGME crude liquid 8a obtained from the reaction tower contains unreacted methanol, propylene oxide, tertiary amine of the catalyst, and the like.

[0819] The obtained PGME crude liquid 8a was supplied to a distillation column for the purpose of purification. Then, distillation was repeated several times to obtain a treated liquid containing PGME (treated liquid 8A).

[0820] The compounds (B) contained in the obtained PGME-containing treatment liquid (treatment liquid 8A) are the following compounds. The contents of these compounds in the treatment liquid all satisfy the requirement (b) (see Table 2).

[0821] [Chemical formula 55]

[0822]

[0823] <Synthesis Example 9>

[0824] Synthesis of a treatment solution containing MMP (methyl 3-methoxypropionate) (treatment solution 8A)

[0825] (Process 1)

[0826] By the method described in Japanese Patent Application Laid-Open No. 2007-63209, methanol, potassium tert-butoxide (KOt-Bu) as a basic catalyst, and 74.0 g (0.86 mol) of methyl acrylate were weighed and slowly added dropwise from a dropping funnel over about 1 hour. At this time, if a small amount of methyl acrylate is added dropwise, heat is generated, so the reaction temperature is controlled to 40° C. while cooling in ice water. After the addition is completed, heating and stirring are performed at 40° C. for 1 hour, and the total reaction time is set to 2 hours.

[0827] Then, phosphoric acid was added, and after confirming neutrality with pH test paper, the mixture was stirred at room temperature for 30 minutes. After neutralization, suction filtration was performed, and the solid matter of the neutralized salt of the catalyst was filtered and separated to obtain a crude liquid containing MMP (hereinafter referred to as "MMP crude liquid") 9a.

[0828] (Process 2)

[0829] In step 1, the MMP crude liquid 9a obtained from the reaction tower contains unreacted methanol, methyl acrylate, and the like.

[0830] The obtained MMP crude liquid 9a was supplied to a distillation column for the purpose of purification, and then the distillation was repeated several times to obtain a treated liquid containing MMP (treated liquid 9A).

[0831] The compounds (B) contained in the obtained MMP-containing treatment liquid (treatment liquid 9A) were the following compounds. The contents of these compounds in the treatment liquid all satisfied the requirement (b) (see Table 2).

[0832] [Chemical formula 56]

[0833]

[0834] The obtained treatment liquids 1A to 1Q, treatment liquid 2A, treatment liquids 3A to 3G, treatment liquids 4A to 4E, treatment liquids 5A to 5E, treatment liquids 6A to 6E, treatment liquids 7A to 7G, treatment liquid 8A, and treatment liquid 9A are shown in Tables 1-1 to 1-6 described later. Hereinafter, Tables 1-1 to 1-6 are collectively referred to as Table 1.

[0835] [Measurement by SP-ICP-MS method]

[0836] 1) Preparation of standard substances

[0837] Ultrapure water was measured and placed in a clean glass container, metal particles of the measurement target having a median diameter of 50 nm were added to a concentration of 10,000 particles / ml, and the resulting dispersion was treated in an ultrasonic cleaner for 30 minutes and used as a standard substance for measuring transmission efficiency.

[0838] 2) SNP-ICP-MS device used

[0839] Manufacturer: PerkinElmer

[0840] Model: NexION350S

[0841] 3) SNP-ICP-MS measurement conditions

[0842] SNP-ICP-MS used a PFA coaxial sprayer, a quartz cyclone spray chamber, and a quartz torch injector with an inner diameter of 1 mm, and sucked the test liquid at about 0.2 mL / min. The cleaning of the cellulase using ammonia was performed with an oxygen addition of 0.1 L / min and a plasma power of 1600 W. The time resolution was 50 us for analysis.

[0843] The content of metal particles and the content of metal atoms were measured using the following analysis software provided by the manufacturer.

[0844] ·Content rate of metal particles: Syngistix Nano Application Module for Nanoparticle Analysis "SP-ICP-MS"

[0845] ·Metal atom content: Syngistix for ICP-MS software

[0846] The results are shown in Table 1 described later.

[0847] [Determination of the content of the chemical formula compound (A), compound (B) and inorganic substance (C)]

[0848] The components used in the examples and comparative examples were measured by GC / MS (Gas Chromatograph / Mass Spectrometer), LC / MS (Liquid Chromatograph / Mass Spectrometer), NMR (Nuclear Magnetic Resonance), and IC (Ion Chromatography). The organic matter was measured by GC / MS, LC / MS, and NMR, and the inorganic matter was analyzed by IC.

[0849] [GC / MS] (Gas Chromatography Mass Spectrometry)

[0850] (Measurement conditions)

[0851] Device: GCMS-2020 manufactured by Shimadzu Corporation

[0852] [LC / MS] (Liquid Chromatography Mass Spectrometry)

[0853] (Measurement conditions)

[0854] Apparatus: Made by Thermo Fisher Scientific, Inc.

[0855] "UPLC-H-Class, Xevo G2-XS QTof"

[0856] [NMR] (Nuclear Magnetic Resonance)

[0857] (Measurement conditions)

[0858] Device: AL400 model manufactured by JEOL Ltd.

[0859] Determination of the core: 1 H

[0860] Solvent: CDCl3

[0861] [IC] (Ion chromatography)

[0862] (Measurement conditions)

[0863] Device: "HIC-SP" manufactured by SHIMADZU CORPORATION.

[0864] The content of each compound is shown in Table 1 described later.

[0865] In addition, the columns of "S", "A1", "B", "N" and "K" in the inorganic substance (C) in Table 1 respectively represent the content rates of the inorganic substance containing S, the inorganic substance containing Al, the inorganic substance containing B, the inorganic substance containing N, and the inorganic substance containing K.

[0866] [Measurement of dissolution rate (ER) of resist film]

[0867] An organic anti-reflection film ARC29A (manufactured by Nissan Chemical Corporation) was coated on a silicon wafer and baked at 205°C for 60 seconds to form an anti-reflection film with a thickness of 78 nm. Then, a commercially available product FAiRS-9101A12 (ArF resist composition manufactured by FUJIFILM Electronic Materials Co., Ltd.) was coated using a spin coater and baked at 100°C for 60 seconds. The obtained wafer was subjected to an ArF excimer laser scanner (NA 0.75) at 25 [mJ / cm 2] The whole wafer was exposed. Then, it was heated at 120°C for 60 seconds. The wafer was cut into 2 cm × 2 cm pieces and immersed in each treatment solution listed in Table 1 at 23°C for 10 minutes. The film thickness before and after immersion was measured by an optical film thickness measuring instrument ellipsometer and the dissolution rate (ER) was calculated.

[0868] Table 1 shows the results.

[0869] [Defect suppression performance (determination of the number of defects)]

[0870] The number of particles with a diameter of 32 nm or more (hereinafter referred to as "defects") on the surface of a silicon substrate with a diameter of 300 mm was measured by a wafer surface inspection device (SP-5; manufactured by KLA Tencor). Next, the silicon substrate was placed on a rotary spraying device, and while being rotated, various processing liquids listed in Table 1 were sprayed onto the surface of the silicon substrate at a flow rate of 1.5 L / min. Then, the sample was rinsed and dried. For the obtained sample, the number of defects on the surface of the silicon substrate was measured again using the above-mentioned device (SP-5), and the difference from the initial value was set as the number of defects. The results of evaluating the obtained number of defects according to the following criteria are shown in Table 1. In the following criteria, evaluation D achieves the defect suppression performance required as a processing liquid for semiconductor manufacturing.

[0871] A: The number of defects is 50 or less.

[0872] B: The number of defects is more than 50 and 100 or less.

[0873] C: The number of defects is more than 100 and 500 or less.

[0874] D: The number of defects is more than 500 and 1000 or less.

[0875] E: The number of defects exceeds 1,000.

[0876]

[0877]

[0878]

[0879]

[0880]

[0881]

[0882] [Table 2]

[0883]

[0884] <Purification Method of Treatment Liquids 7B to 7D and Treatment Liquids 7F to 7G>

[0885] The crude liquid 7a of cyclohexanone (CyHx) obtained above was purified by the method shown below, thereby obtaining treatment liquids 7B to 7D and treatment liquids 7F to 7G shown in Table 1.

[0886] As a purification method, a method having the Figure 2 The manufacturing apparatus of the structure of the manufacturing apparatus shown in the figure was selected, and the number of distillation steps or the filtering method (pore size, material) were selected, thereby obtaining the treatment liquids 7B to 7D and treatment liquids 7F to 7G of different purities. As the filtering method, the filter shown in the following Table 3 was used as the filter used in the filtering device equipped in the above-mentioned manufacturing apparatus to adjust the purity of the treatment liquid.

[0887] In addition, before the crude liquid 7a was purified by the purification method, the manufacturing apparatus was cleaned with a cleaning liquid. As a cleaning method, the treatment liquid 7E (cyclohexanone) shown in Table 1 was used as the cleaning liquid, and the operation of passing the treatment liquid 7E through the filter was repeated 3 times by 10 cycles, which was set as one set.

[0888]

[0889] In Table 3, Nylon, PTFE (polytetrafluoroethylene) and UPE (Ultra High Molcular Weight PolyEthylene) respectively represent filters with nylon as the main component, filters with PTFE as the main component and filters with UPE as the main component. In addition, in IEX-PTFE sufric acid and IEX-PTFE carboxylic acid, IEX represents an ion exchange group, and refers to filters formed by modifying the surface of PTFE with sulfonic acid or carboxylic acid.

[0890] <Preparation of Resist Pattern>

[0891] [Examples 101 to 112, Comparative Example 101, Comparative Example 102]

[0892] An organic anti-reflection film ARC29A (manufactured by Nissan Chemical Corporation) was coated on a silicon wafer and baked at 205°C for 60 seconds to form an anti-reflection film with a thickness of 78 nm. On top of it, a commercially available product FAiRS-9101A12 (ArF resist composition manufactured by FUJIFILM Electronic Materials Co., Ltd.) was coated using a spin coater and baked at 100°C for 60 seconds to form a resist film with a thickness of 150 nm. The obtained wafer was subjected to an ArF excimer laser scanner (NA 0.75) at 25 [mJ / cm 2 Then, after heating at 120° C. for 60 seconds, development (negative tone development) was performed for 30 seconds using each of the treatment solutions listed in Table 4 to obtain an L / S pattern.

[0893] In Examples 105 to 107, after the development, rinsing was performed for 30 seconds using each of the treatment liquids described in Table 4 to obtain an L / S pattern.

[0894] [Examples 113 to 119]

[0895] An organic antireflection film ARC29A (manufactured by Nissan Chemical Corporation) was coated on the silicon wafer and baked at 205°C for 60 seconds to form an antireflection film with a thickness of 78 nm. Then, in order to improve the coating properties, a pre-wetting step of applying the treatment liquid described in Table 3 was performed. Then, a commercially available FAiRS-9101A12 (manufactured by FUJIFILM Electronic Materials C o ., Ltd.) and baked at 100°C for 60 seconds to form a resist film with a thickness of 150 nm. The obtained wafer was irradiated with an ArF excimer laser scanner (NA0.75) at 25 [mJ / cm 2 Then, after heating at 120° C. for 60 seconds, the pattern was developed (negative development) for 30 seconds using the processing solution described in Table 4, and the obtained pattern was rinsed and cleaned using the processing solution described in Table 1 to obtain an L / S pattern.

[0896] [Lithography performance]

[0897] After the pattern is formed, the surface and space of the line pattern are observed using a length-measuring scanning electron microscope (S9380II manufactured by Hitachi, Ltd.). The smaller the value of the pattern size formed, the better the performance. In the following benchmarks, the evaluation D achieves the photolithography performance required as a resist pattern.

[0898] Table 4 shows the evaluation results.

[0899] AL / S=less than 80nm

[0900] BL / S = 80nm or more and less than 120nm

[0901] CL / S = 120nm or more and less than 150nm

[0902] DL / S = 150nm or more and less than 200nm

[0903] EL / S=200nm or more

[0904]

[0905] <Examples 201 to 202, Comparative Example 201>

[0906] Dimethyl sulfoxide (Wako Pure Chemical Industries, Ltd.) was prepared and purified by the method described in Japanese Patent Application Laid-Open No. 2007-254168, and was used for the preparation of the treatment liquid after confirming that the contents of Na, Ca, and Fe were each less than 10 ppb by mass.

[0907] Embodiment 201

[0908] Treatment liquid X-1 was prepared by mixing 90.5 parts by mass of the treatment liquid 1A of Example 1 and 9.5 parts by mass of the dimethyl sulfoxide obtained above.

[0909] The treatment liquid X-1 contains, in addition to the treatment liquid 1A and the above-mentioned dimethyl sulfoxide, two or more compounds (B) and inorganic substances (C) satisfying the requirement (b), and the total content of the compound (B) is 10 -10 ~0.1 mass %, the ratio P of the compound (B) represented by formula I to the inorganic substance (C) is 10 3 ~10 -6 When the same evaluation as in Example 1 and Example 101 was carried out using the processing liquid X-1, the same defect suppression performance as in Example 1 and the same lithography performance as in Example 101 were obtained.

[0910] Embodiment 202

[0911] Treatment liquid X-2 was prepared by mixing 95 parts by mass of the treatment liquid 1A of Example 1 and 5 parts by mass of the dimethyl sulfoxide obtained above.

[0912] The treatment liquid X-2 contains, in addition to the treatment liquid 1A and the above-mentioned dimethyl sulfoxide, two or more compounds (B) and inorganic substances (C) satisfying the requirement (b), and the total content of the compound (B) is 10 -10 ~0.1 mass %, the ratio P of the compound (B) represented by formula I to the inorganic substance (C) is 10 3 ~10 -6 When the same evaluation as in Example 1 and Example 101 was carried out using the processing liquid X-2, the same defect suppression performance as in Example 1 and the same lithography performance as in Example 101 were obtained.

[0913] Comparative Example 201

[0914] Treatment liquid X-3 was prepared by mixing 85 parts by mass of the solution of treatment liquid 1A of Example 1 and 15 parts by mass of dimethyl sulfoxide obtained above. The same evaluation as in Example 1 and Example 101 was performed using treatment liquid X-3. The same results as in Example 1 were obtained, but treatment liquid remained after rinsing, and it took time to dry.

[0915] <Examples 301 to 307>

[0916] The first treatment liquid and the second treatment liquid shown in Table 5 described later were mixed in the ratio shown in the table to prepare treatment liquids 101 to 106. In addition, treatment liquid 107 shown in Table 5 is treatment liquid 9A prepared as described above. For these treatment liquids 101 to 107, the defect suppression performance was evaluated by the same method as the above method. In addition, the resist saving when these treatment liquids were used as pre-wetting liquids was evaluated. In addition, the performance when these treatment liquids were used as rinse liquids after ashing or p-CMP was evaluated. The results are shown in Table 5.

[0917] [Resist saving]

[0918] The resist saving property when each treatment liquid was used as a pre-wetting solution was evaluated by the following method. In addition, in this specification, having excellent resist saving property means having excellent uniformity and excellent film thickness controllability, and it is known that deterioration of lithography performance or generation of defects can be suppressed thereby.

[0919] The resist composition 1 used is as follows.

[0920] <Resist Composition 1>

[0921] The acid-decomposable resin, photoacid generator, quencher, hydrophobic resin, and solvent shown below were mixed to prepare a resist composition 1 having a solid content concentration of 3.5% by mass.

[0922] Acid-decomposable resin shown below: 100 parts by mass

[0923] [Chemical formula 57]

[0924]

[0925] The weight average molecular weight (Mw) of the acid-decomposable resin is 7500, and the numerical value described in each repeating unit means mol %.

[0926] The photoacid generator shown below: 8 parts by mass

[0927] [Chemical formula 58]

[0928]

[0929] The following four quenchers: 5 parts by mass (total)

[0930] [Chemical formula 59]

[0931]

[0932] The mass ratios of the quenchers are 0.1:0.3:0.3:0.2 from the left. Among the four quenchers, the weight average molecular weight (Mw) of the polymer type quencher on the right is 5000. The numerical values ​​described in each repeating unit are molar ratios.

[0933] Two hydrophobic resins shown below: 4 parts by mass (total)

[0934] [Chemical formula 60]

[0935]

[0936] The mass ratio of the hydrophobic resins is 0.5:0.5 from the left. In addition, of the two hydrophobic resins, the weight average molecular weight (Mw) of the hydrophobic resin on the left is 7000, and the weight average molecular weight (Mw) of the hydrophobic resin on the right is 8000. In addition, in each hydrophobic resin, the numerical value recorded in each repeating unit refers to the molar ratio.

[0937] Solvent 1:

[0938] PGMEA (manufactured by WAKOSHA Incorporated): 3 parts by mass

[0939] CyHx (cyclohexanone) (manufactured by WAKOSHA Incorporated): 600 parts by mass

[0940] GBL (γ-butyrolactone) (manufactured by WAKOSHA Incorporated): 100 parts by mass.

[0941] <Resist Composition 2>

[0942] Resist Composition 2 was prepared under the same conditions as in Resist Composition 1 except that the following solvent 2 was used instead of the above-mentioned solvent 1 (PGMEA:CyHx:GBL=3 parts by mass:600 parts by mass:100 parts by mass).

[0943] Solvent 2:

[0944] Treatment liquid 4A (PGMEA): 3 parts by mass

[0945] Treatment liquid 7D (CyHx): 600 parts by mass

[0946] GBL (γ-butyrolactone) (manufactured by WAKOSHA Incorporated): 100 parts by mass.

[0947] <Uniformity>

[0948] First, as a control, the above-mentioned resist composition 1 (or resist composition 2) was directly coated on a silicon wafer with a diameter of about 30 cm (12 inches) having an anti-reflective film. In addition, a spin coater (trade name "LITHIUS", manufactured by Tokyo Electron Limited) was used for coating. The obtained resist film was baked at 90°C. Regarding the resist film after baking, a 59-point map was measured using a film thickness measuring device Lambda Ace manufactured by Dainippon Screen Co., Ltd., and it was confirmed that no coating spots were generated. In addition, coating spots refer to a state in which there is no unevenness in the thickness of the resist film when 59 measuring points are extracted in a circle from the resist film of the measured object and the measurement results of the thickness of the resist film at each measuring point are arranged two-dimensionally for each measuring point and observed.

[0949] Next, a silicon wafer with a diameter of about 30cm (12 inches) having an anti-reflection film is prepared separately, and each treatment solution is added dropwise. Then, the same amount of resist composition 1 (or resist composition 2) as the control is applied and baked at 90°C. The obtained resist film is observed by the same method as above, and it is confirmed that no coating spots are generated. Next, the resist composition 1 (or resist composition 2) used is reduced to 50% and 30% by mass of the control, and the same test as above is performed to investigate whether coating spots are generated.

[0950] The results were evaluated based on the following criteria and are shown in Table 5.

[0951] AA: No coating unevenness occurred when the amount of the resist composition used was reduced to 30% by mass of the control and when it was reduced to 50% by mass.

[0952] A: Even when the amount of the resist composition used was reduced to 50% by mass of the control, coating unevenness did not occur, but when it was reduced to 30% by mass of the control, coating unevenness occurred.

[0953] B: Coating unevenness occurred in both the case where the amount of the resist composition used was reduced to 30% by mass of the control and the case where the amount was reduced to 50% by mass.

[0954] <Film Thickness Controllability>

[0955] Each treatment liquid is dropped onto a silicon wafer having a diameter of about 30 cm (12 inches) and an anti-reflective film. Then, the above-mentioned resist composition 1 (or resist composition 2) is directly applied in such a way that the thickness of the obtained resist film becomes 8.5 nm. In addition, a spin coater (trade name "LITHIUS", manufactured by Tokyo Electron Limited) is used for coating. The obtained resist film is baked at 90°C. For the resist film after baking, a 59-point map is measured using a film thickness measuring device Lambda Ace manufactured by Dainippon Screen Co., Ltd., and the standard deviation (hereinafter also referred to as "σ") of the thickness of the resist film is calculated. Next, 3σ is calculated from the standard deviation.

[0956] The results were evaluated according to the following criteria and are shown in Table 5.

[0957] A: 3σ is less than 0.15 nm.

[0958] B: 3σ is 0.15 nm or more and less than 0.2 nm.

[0959] C: 3σ is 0.2 nm or more.

[0960] [Rinsing performance after ash removal]

[0961] A 12-inch wafer having the following resist film (film thickness 0.5 μm) was prepared, wherein the resist film was formed by coating resist composition 1 (or resist composition 2) on a silicon wafer and drying by exposure (50 mmH) and heating (220°C). Next, the resist film was ashed and removed using plasma gas under the following conditions. Next, each treatment liquid (treatment liquid 101 to 107) shown in Table 5 was used for cleaning to remove the residue after ashing and removal (ashing residue). Then, the number of defects of the cleaned wafer was counted using SP-2 (manufactured by KLA Tencor), thereby evaluating the rinsing performance of each treatment liquid for the ashing residue.

[0962] [Conditions for ash removal]

[0963] Chip temperature: 250°C

[0964] O2 gas flow rate: 1,000sccm

[0965] Pressure: 70Pa,

[0966] Microwave power: 1kW

[0967] -Evaluation Criteria-

[0968] AA: The number of defects is 50 or less.

[0969] A: The number of defects is more than 50 and less than 80.

[0970] B: The number of defects is more than 80 and 100 or less.

[0971] C: The number of defects is more than 100 and 150 or less.

[0972] D: The number of defects exceeds 150.

[0973] 〔Rinsing performance after p-CMP〕

[0974] The surface of a 12-inch diameter Sematech 845 (copper wiring, barrier metal TaN, oxide film TEOS; manufactured by Sematech) was polished and flattened using CSL9044C (slurry manufactured by FFPS INC.) and then fine polished using BSL8178C (slurry manufactured by FFPS INC.).

[0975] Next, after cleaning with Clean100 (Wako Pure Chemical Industries, Ltd.), each treatment liquid was used as a rinse liquid. Then, the number of defects on the pattern of the Sematech 854 was measured using a pattern defect detector (Com PLUS manufactured by AMAT). The results were evaluated according to the following criteria.

[0976] -Evaluation Criteria-

[0977] AA: The number of defects is 50 or less.

[0978] A: The number of defects is more than 50 and less than 80.

[0979] B: The number of defects is more than 80 and 100 or less.

[0980] C: The number of defects is more than 100 and 150 or less.

[0981] D: The number of defects exceeds 150.

[0982]

Claims

1. A processing liquid for semiconductor manufacturing, comprising: A compound (A) satisfying the following requirement (a); One or more compounds (B) satisfying the following requirement (b); and One or more inorganic substances (C) containing any element selected from Al, B, S, N and K, The total content of compound (B) in the treatment liquid is 10 -10 Mass%~0.1 mass%, The ratio P of the compound (B) represented by the following formula I to the inorganic substance (C) is 10 -3 ~10 -6 , Compound (B) is one or more selected from the following compounds, Requirement (a): a compound selected from alcohol compounds, ketone compounds and ester compounds, the content of which in the treatment liquid is 90.0% by mass to 99.9999999% by mass; Requirement (b): A compound having 6 or more carbon atoms selected from alcohol compounds, ketone compounds, ester compounds, ether compounds and aldehyde compounds, and containing 10 -11 % to 0.1% by mass of the compound, P = [total mass of inorganic substances (C)] / [total mass of compound (B)] Formula I.

2. The semiconductor manufacturing processing liquid according to claim 1, wherein The compound (A) is an alcohol compound or a ketone compound.

3. The semiconductor manufacturing processing liquid according to claim 1, wherein Compound (B) is one or more selected from the following compounds, 4. The semiconductor manufacturing processing liquid according to any one of claims 1 to 3, wherein The inorganic substance (C) is a compound containing any element selected from the group consisting of Al, B and S.

5. The semiconductor manufacturing processing liquid according to any one of claims 1 to 3, wherein The content of each of the one or more inorganic substances (C) contained in the semiconductor manufacturing process liquid is 0.0001 ppb by mass to 100 ppb by mass.

6. The semiconductor manufacturing processing liquid according to any one of claims 1 to 3, wherein The content of each of the one or more inorganic substances (C) contained in the semiconductor manufacturing process liquid is 0.001 ppb by mass to 100 ppb by mass. 7 . The semiconductor manufacturing processing liquid according to claim 1 , comprising Na, Ca and Fe, wherein the content of each atom is 0.01 mass ppt to 1000 mass ppb.

8. The semiconductor manufacturing processing liquid according to any one of claims 1 to 3, wherein The total content of the metal particles measured by the SNP-ICP-MS method is 0.001 to 100 mass ppt.

9. The semiconductor manufacturing processing liquid according to any one of claims 1 to 3, wherein The total content of the metal particles measured by the SNP-ICP-MS method is 1 to 100 mass ppt. 10 . A semiconductor manufacturing process liquid comprising two or more semiconductor manufacturing process liquids according to claim 1 .

11. The semiconductor manufacturing processing liquid according to any one of claims 1, 2, 3, and 10, wherein The semiconductor manufacturing processing liquid is a developer.

12. The semiconductor manufacturing processing liquid according to any one of claims 1, 2, and 10, wherein The semiconductor manufacturing processing liquid is a rinse liquid.

13. The semiconductor manufacturing processing liquid according to any one of claims 1, 2, and 10, wherein The semiconductor manufacturing processing liquid is a pre-wetting liquid.

14. A method for producing a semiconductor manufacturing process liquid, which is a method for producing the semiconductor manufacturing process liquid according to any one of claims 1 to 13, the method for producing a semiconductor manufacturing process liquid comprising: allowing one or more raw materials to react in the presence of a catalyst to synthesize compound (A) and obtain a crude liquid containing compound (A), compound (B) and inorganic substance (C); and The crude liquid is purified.

15. A pattern forming method, comprising: A step of coating an actinic ray-sensitive or radiation-sensitive resin composition on a substrate to form an actinic ray-sensitive or radiation-sensitive film; A step of exposing the actinic ray-sensitive or radiation-sensitive film to light; and A step of treating the substrate or the actinic ray-sensitive or radiation-sensitive film using the semiconductor manufacturing processing liquid according to any one of claims 1 to 13.

16. The pattern forming method according to claim 15, wherein: The step of processing the substrate or the actinic ray-sensitive or radiation-sensitive film using the semiconductor manufacturing processing liquid at least includes a step of developing the actinic ray-sensitive or radiation-sensitive film using the semiconductor manufacturing processing liquid as a developer.

17. The pattern forming method according to claim 15 or 16, wherein: The step of processing the substrate or the actinic ray-sensitive or radiation-sensitive film using the semiconductor manufacturing processing liquid at least includes a step of cleaning the actinic ray-sensitive or radiation-sensitive film using the semiconductor manufacturing processing liquid as a rinse liquid.

18. The pattern forming method according to claim 15 or 16, wherein: The step of processing the substrate or the actinic ray-sensitive or radiation-sensitive film using the semiconductor manufacturing processing liquid includes at least a step of processing the substrate using the semiconductor manufacturing processing liquid as a pre-wetting liquid.

19. The pattern forming method according to claim 15 or 16, wherein: As the semiconductor manufacturing processing liquid, a semiconductor manufacturing processing liquid having a dissolution rate of 0.0016 nm / sec to 0.33 nm / sec at 23° C. when the actinic ray-sensitive or radiation-sensitive film before exposure is immersed is used.

20. A method for manufacturing an electronic device, comprising the pattern forming method according to any one of claims 15 to 19.

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