Semiconductor manufacturing processing fluids

Abstract

To provide a processing liquid for semiconductor manufacturing capable of manufacturing a fine resist pattern or a fine semiconductor element by suppressing a deterioration in lithography performance and an occurrence of a defect.SOLUTION: A processing liquid for semiconductor manufacturing is provided, containing one kind of a compound (A) selected from butyl acetate, 1-hexanol, 4-methyl-2-pentanol, propylene glycol monomethyl ether acetate, isopropanol, cyclohexanone, propylene glycol monomethyl ether and methyl 3-methoxypropionate, one or more kinds of compounds (B) satisfying specific requirements, and one or more kinds of inorganic materials (C) containing any element selected from Al, B, S, N and K in respective specific content, and is any of developer solution, rinse solution, pre-wet solution, and stripping solution, a percentage P expressed by formula I is 103 to 10-6, and the total content of metal particles measured by an SNP-ICP-MS method is 0.001 to 100 mass ppt. (Formula I) P=(total mass of inorganic substance (C)) / (total mass of compound (B)).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to processing liquids for semiconductor manufacturing, such as developing liquids, rinse liquids, pre-wet liquids, and stripping liquids, which are used in the manufacturing process of semiconductor devices, methods for manufacturing the same, pattern formation methods, and electronic device manufacturing methods. [Background technology]

[0002] The manufacturing process of semiconductor devices includes various steps such as lithography, etching, ion implantation, and stripping. These generally include a process of treating unwanted organic and inorganic substances with a processing liquid after each step or before moving on to the next step. Examples of such processes include a development process in which a resist film after exposure is treated with a developer, a stripping process in which resist remaining on the substrate surface after substrate processing is treated with a stripping liquid, and a rinsing process in which a rinse liquid is used to further clean the surface after the stripping or development process.

[0003] The various processing solutions used in the manufacturing process of semiconductor devices, such as developing solutions, rinse solutions, pre-wet solutions, and stripping solutions (hereinafter also referred to as "processing solutions for semiconductor manufacturing"), are required to be highly pure. As semiconductors become increasingly miniaturized and functionally sophisticated, market demand for high-purity processing solutions in general is increasing, and this market is expected to expand in the future.

[0004] A basic requirement for a high-purity semiconductor manufacturing processing solution is that it has a low metal concentration and a low particle concentration. For example, Japanese Patent Application Laid-Open No. 2015-84122 discloses a technology capable of reducing particle generation in organic developers. Furthermore, metals in processing solutions can cause a phenomenon known as migration, in which metals diffuse into target materials during processing. Migration can impede the transmission of electrical signals and lead to defects such as short circuits. Furthermore, the metal itself can become a nucleus that remains as residue after processing, which can degrade lithography performance, cause defects, and adversely affect the formation of fine resist patterns or semiconductor elements. Given this background, there is a strong demand for even higher purity processing solutions for semiconductor manufacturing. Summary of the Invention [Problem to be solved by the invention]

[0005] The cutting-edge processing solutions currently used in the semiconductor manufacturing industry have achieved a fairly high level of purity. For example, a rinse solution using isopropanol (IPA) from FEUS, which boasts high purity and low metal content, has a total metal concentration of tens to hundreds of parts per trillion (ppt). However, the performance required in the future will require a metal concentration of, for example, 10 ppt or less, and current performance will not be sufficient.

[0006] The present invention has been developed against this background, and aims to provide a processing solution for semiconductor manufacturing that suppresses deterioration of lithography performance and the occurrence of defects and enables the manufacturing of fine resist patterns or fine semiconductor elements, and to provide a method for manufacturing the processing solution for semiconductor manufacturing. Another aim of the present invention is to provide a pattern formation method using the processing solution for semiconductor manufacturing, and a method for manufacturing semiconductor elements that includes the pattern formation method. [Means for solving the problem]

[0007] In one aspect, the present invention is as follows. [1] One compound (A) that satisfies the following requirement (a), one or more compounds (B) that satisfy the following requirement (b); A processing solution for semiconductor manufacturing, comprising one or more inorganic substances (C) containing any one element selected from Al, B, S, N, and K, The total content of the compound (B) in the treatment solution is 10 -10 ~0.1% by mass, The ratio P of the compound (B) represented by the following formula I to the inorganic substance (C) is 10 3 ~10 -6 A processing liquid for semiconductor manufacturing. Requirement (a): The compound is selected from alcohol compounds, ketone compounds, and ester compounds, and the content of the compound in the treatment liquid is 90.0 to 99.9999999% by mass. Requirement (b): The compound is selected from alcohol compounds, ketone compounds, ester compounds, ether compounds, and aldehyde compounds having 6 or more carbon atoms, and the content of the compound in the treatment liquid is 10 -11 ~0.1% by mass of the compound. P = [total mass of inorganic substances (C)] / [total mass of compounds (B)] Formula I [2] The treating solution for semiconductor manufacturing according to [1], wherein the inorganic substance (C) is a compound containing any element selected from Al, B, and S.

[0008] [3] The processing solution for semiconductor manufacturing according to [1] or [2], wherein the content of each of the one or more inorganic substances (C) contained in the processing solution for semiconductor manufacturing is 0.0001 to 100 ppb by mass.

[0009] [4] The processing solution for semiconductor manufacturing according to any one of [1] to [3], wherein the content of each of the one or more inorganic substances (C) contained in the processing solution for semiconductor manufacturing is 0.001 to 100 mass ppb.

[0010] [5] The treating solution for semiconductor manufacturing according to any one of [1] to [4], which contains Na, Ca, and Fe, and the content of each element is 0.01 mass ppt to 1000 mass ppb.

[0011] [6] The treating solution for semiconductor manufacturing according to any one of [1] to [5], wherein the total content of metal particles measured by SNP-ICP-MS is 0.001 to 100 mass ppt.

[0012] [7] The treating solution for semiconductor manufacturing according to any one of [1] to [6], wherein the total content of metal particles measured by SNP-ICP-MS is 1 to 100 mass ppt.

[0013] [8] The treating solution for semiconductor manufacturing according to any one of [1] to [7], which contains at least one compound represented by the following formulae I to V as the compound (B):

[0014] [ka]

[0015] 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. In Formula II, R3 and R4 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, or a cycloalkenyl group, or are bonded to each other to form a ring, provided that R3 and R4 are not both hydrogen atoms. In formula III, R5 represents an alkyl group or a cycloalkyl group. 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. In Formula V, R8 and R9 each independently represent an alkyl group or a cycloalkyl group, or are bonded to each other to form a ring, and L represents a single bond or an alkylene group.

[0016] [9] The ratio Q of the compound (A) and the compound (B) represented by the following formula II is 10 4 ~10 10 The treating solution for semiconductor manufacturing according to any one of [1] to [8], wherein Q = [total mass of compound (A)] / [total mass of compound (B)] Formula II

[10] A processing solution for semiconductor manufacturing, comprising two or more processing solutions for semiconductor manufacturing according to any one of [1] to [9].

[0017]

[11] The processing solution for semiconductor manufacturing according to any one of [1] to

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

[0018]

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

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

[0019]

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

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

[0020]

[14] A method for producing a processing solution for semiconductor manufacturing according to any one of [1] to

[13] , comprising: synthesizing compound (A) by reacting one or more raw materials in the presence of a catalyst to obtain a crude liquid containing compound (A), compound (B) and inorganic substance (C); and purifying the crude liquid. A method for producing a processing solution for semiconductor manufacturing, comprising:

[0021]

[15] a step of applying the actinic ray-sensitive or radiation-sensitive resin composition to a substrate to form an actinic ray-sensitive or radiation-sensitive film; a step of exposing the actinic ray- or radiation-sensitive film to light; and a step of treating the substrate or the actinic ray-sensitive or radiation-sensitive film with the treatment solution for semiconductor manufacturing according to any one of [1] to

[13] ; A pattern forming method comprising:

[0022]

[16] The pattern formation method according to

[15] , wherein the step of treating the substrate or the actinic ray-sensitive or radiation-sensitive film with the processing solution for semiconductor manufacturing comprises at least a step of developing the actinic ray-sensitive or radiation-sensitive film using the processing solution for semiconductor manufacturing as a developer.

[0023]

[17] The pattern formation method according to

[15] or

[16] , wherein the step of treating the substrate or the actinic ray-sensitive or radiation-sensitive film with the processing solution for semiconductor manufacturing comprises at least a step of rinsing the actinic ray-sensitive or radiation-sensitive film using the processing solution for semiconductor manufacturing as a rinse liquid.

[0024]

[18] The pattern formation method according to any one of

[15] to

[17] , wherein the step of treating the substrate or the actinic ray-sensitive or radiation-sensitive film with the treatment liquid for semiconductor manufacturing comprises at least a step of treating the substrate with the treatment liquid for semiconductor manufacturing as a pre-wet liquid.

[0025]

[19] The method for forming a pattern according to any one of

[15] to

[18] , wherein the treatment liquid for semiconductor production is a treatment liquid for semiconductor production in which the actinic ray-sensitive or radiation-sensitive film before exposure is immersed at 23°C and the dissolution rate is 0.0016 to 0.33 nm / sec.

[0026]

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

[15] to

[19] . [Effects of the Invention]

[0027] The present invention makes it possible to provide a processing solution for semiconductor manufacturing that suppresses deterioration of lithography performance and the occurrence of defects and enables the manufacturing of fine resist patterns or fine semiconductor elements, and to provide a method for manufacturing the processing solution for semiconductor manufacturing.The present invention also makes it possible to provide a pattern formation method using the processing solution for semiconductor manufacturing, and a method for manufacturing semiconductor elements that includes the pattern formation method. [Brief explanation of the drawings]

[0028] [Figure 1] FIG. 1 is a schematic diagram showing one embodiment of a manufacturing apparatus that can be used in a method for manufacturing a treatment liquid according to an embodiment of the present invention. [Figure 2] FIG. 2 is a schematic diagram showing another embodiment of a manufacturing apparatus that can be used in the method for manufacturing a treatment liquid according to an embodiment of the present invention. Embodiment

[0029] In the description of groups (atomic groups) in this specification, when a notation does not specify whether the group is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups. For example, the term "alkyl group" encompasses not only alkyl groups without a substituent (unsubstituted alkyl groups) but also alkyl groups with a substituent (substituted alkyl groups).

[0030] In addition, the terms "actinic rays" or "radiation" in this specification refer to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet (EUV) rays, X-rays, or electron beams (EB). In addition, in the present invention, "light" refers to actinic rays or radiation.

[0031] Furthermore, unless otherwise specified, the term "exposure" in this specification includes not only exposure using a mercury lamp, far ultraviolet light represented by an excimer laser, X-rays, EUV light, and the like, but also drawing using particle beams such as electron beams and ion beams.

[0032] In this specification, "(meth)acrylate" means "at least one of acrylate and methacrylate." Also, "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid." Also, in this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. Hereinafter, embodiments of the present invention will be described in detail.

[0033] <Semiconductor manufacturing processing liquid> In the present invention, as described above, the "processing liquid for semiconductor manufacturing" is a processing liquid used to process organic matter after the completion of each process or before moving to the next process in the manufacturing process of semiconductor devices, which process includes a lithography process, an etching process, an ion implantation process, a stripping process, etc., and specifically, is a processing liquid used as a developer, a rinse liquid, a pre-wet liquid, a stripping liquid, etc.

[0034] The processing solution for semiconductor manufacturing of the present invention (hereinafter, also referred to as "the processing solution of the present invention") contains one compound (A) satisfying the following requirement (a), at least one compound (B) satisfying the following requirement (b), and at least one inorganic substance (C) containing any element selected from Al, B, S, N, and K. 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 mass %. Requirement (b): The compound is selected from alcohol compounds, ketone compounds, ester compounds, ether compounds, and aldehyde compounds having 6 or more carbon atoms, and the content of the compound in the processing solution of the present invention is 10 -11 ~0.1% by mass of the compound.

[0035] 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, for example, preferably 99.999 to 99.9999999 mass %, and particularly preferably 99.9999 to 99.9999999 mass %.

[0036] Furthermore, the treatment liquid of the present invention may be a combination system of compound (A) and other compounds, and in that case, the content of the other compounds is, for example, preferably 0.01 to 5.00 mass %, more preferably 0.1 to 2.00 mass %. In this case, the other compound may be, for example, dimethyl sulfoxide.

[0037] In the processing solution of the present invention, the compound (B) is contained as an impurity, and the total content of the compound (B) is 10% or less based on the total mass of the processing solution. -10 The total content of the compound (B) is the content described in the requirement (b), that is, the content is 10 to 0.1% by mass. -11 When one type of compound (B) is present in the treatment solution in a range of 0.1 mass % or less, this refers to the content of this one type of compound (B). When two or more types of compound (B) that satisfy the content requirement described in requirement (b) are present, this refers to the total content of these two or more types of compound (B).

[0038] The content of the compound (B) described in the requirement (b) is preferably 10 -10 ~10 -4 % by mass, more preferably 10 -10 ~10 -5 It is expressed in mass%.

[0039] In the treatment liquid of the present invention, the inorganic substance (C) containing any element selected from Al, B, S, N and K is mixed in during the synthesis of the treatment liquid of the present invention and is mainly derived from the catalyst. In one embodiment, the treatment liquid of the present invention contains a compound containing any element selected from Al, B, and S as the inorganic substance (C).

[0040] Although most of the compound (B) and inorganic substance (C) are removed in the purification step of the treatment liquid, trace amounts remain in the purified treatment liquid.

[0041] The present invention was developed based on the finding that the ratio of the compound (B) to the inorganic substance (C) contained in a processing solution for semiconductor manufacturing has a significant effect on lithography performance and defect performance. The present invention is based on the finding that the ratio of the inorganic substance (C) to the compound (B) has a P value represented by the following formula I of 10 3 ~10 -6 One of the features is that the range is

[0042] P = [total mass of inorganic substances (C)] / [total mass of compounds (B)] Formula I The ratio P of inorganic matter (C) to compound (B) is 10 3 ~10 -6 When the content of the compound (B) in the treatment solution is within this range, deterioration of lithography performance and the occurrence of defects can be suppressed, and it is possible to provide a fine resist pattern or a fine semiconductor element. Although the mechanism of this phenomenon is not entirely clear, it is presumed that if the balance between the compound (B) and the inorganic substance (C) contained in the treatment solution is disrupted, a peculiar phenomenon that causes deterioration of lithography performance and the occurrence of defects occurs during treatment with each treatment solution, such as a developer, a rinse solution, a pre-wet solution, or a stripper solution.

[0043] The P value, which is the ratio of inorganic (C) to compound (B), as expressed in formula I, is 10 3 ~10 -5 Preferably, 10 2 ~10 -4 It is more preferable that:

[0044] As described above, the compound (B) is present in an amount of 10% by weight based on the total weight of the treatment liquid. -10 Although it is an impurity contained in a small amount in the range of 10 to 0.1 mass %, it is 4 ~10 10 is preferable from the viewpoint of improving lithography performance and suppressing defects.

[0045] Q = [total mass of compound (A)] / [total mass of compound (B)] Formula II Although the mechanism of this phenomenon is not clear, it has been confirmed that the effects of the present invention are further improved when the ratio Q of compound (A) to compound (B) is within the above range.

[0046] The Q value, which is the ratio of compound (A) to compound (B) as represented by formula II, is 10 5 ~10 10 It is more preferable that 6 ~10 10 It is more preferable that:

[0047] 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), and more preferably 0.001 to 100 mass ppb, based on the total mass of the treatment liquid. When the treatment liquid of the present invention contains two or more inorganic substances (C), the content of each of the inorganic substances (C) is preferably 0.0001 to 100 mass ppb, and more preferably 0.001 to 100 mass ppb.

[0048] When the concentration of each of the inorganic substances (C) is 100 mass ppb or less, it is possible to prevent these compounds from remaining on the substrate as nuclei of residual components during processing and becoming the cause of defects.

[0049] On the other hand, it is generally thought that the less inorganic substance (C) there is, the better, but it has been confirmed that defects tend to increase again when the concentration drops below 0.001 mass ppb. Although the mechanism is not entirely clear, it is assumed that when inorganic substance (C) is removed from the substrate, it is removed as a certain amount of ions or compound clumps, which also entrains compound (B). Therefore, if there is too little inorganic substance (C), the removal rate of inorganic substance (C) and compound (B) deteriorates, and they remain on the substrate, which is thought to cause defects.

[0050] 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.

[0051] Examples of alcohol compounds include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 3-methyl-3-pentanol, cyclopentanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, Examples of suitable solvents include alcohols (monohydric alcohols) such as 1-butanol and 3-methoxy-1-butanol; glycol-based solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; and glycol ether-based solvents containing a hydroxyl group such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol), diethylene glycol monomethyl ether, methoxymethylbutanol, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether.

[0052] Examples of the ketone compound include acetone, 1-hexanone, 2-hexanone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, acetylcarbinol, propylene carbonate, γ-butyrolactone, etc. The ketone compound as compound (A) also includes a diketone compound.

[0053] Examples of ester compounds 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.

[0054] In one embodiment, compound (A) may be a mixture of compounds having the same carbon number but different structures, such as isomers. The compound (A) may contain only one type of compound having the same carbon number but different structures, or may contain multiple types of compounds as described above.

[0055] In one embodiment, the compound (A) has a flash point of preferably 80° C. or less, more preferably 75° C. or less, and even more preferably 65° C. or less. The lower limit of the flash point is not particularly limited, but is preferably, for example, 23° C. or more.

[0056] As described above, the compound (B) contained in the treatment liquid of the present invention is a compound selected from alcohol compounds, ketone compounds, ester compounds, ether compounds, and aldehyde compounds having 6 or more carbon atoms, and the treatment liquid of the present invention contains one or more of these compounds. The number of carbon atoms in compound (B) is preferably 6 to 12, and more preferably 6 to 10.

[0057] In one embodiment of the present invention, compound (B) is preferably at least one of the compounds represented by the following formulae I to V.

[0058] [ka]

[0059] 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.

[0060] The alkyl group and cycloalkyl group represented by R1 and R2 are preferably alkyl groups having 1 to 12 carbon atoms and cycloalkyl groups having 6 to 12 carbon atoms, more preferably alkyl groups having 1 to 8 carbon atoms and cycloalkyl groups having 6 to 8 carbon atoms.

[0061] The ring formed by bonding R1 and R2 to each other is a lactone ring, preferably a 4- to 9-membered lactone ring, and more preferably a 4- to 6-membered lactone ring. R1 and R2 satisfy the relationship such that the compound represented by formula I has 6 or more carbon atoms.

[0062] In Formula II, R3 and R4 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, or a cycloalkenyl group, or are bonded to each other to form a ring, provided that R3 and R4 are not both hydrogen atoms.

[0063] The alkyl group represented by R3 and R4 is, for example, preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms.

[0064] The alkenyl group represented by R3 and R4 is, for example, preferably an alkenyl group having 2 to 12 carbon atoms, more preferably an alkenyl group having 2 to 8 carbon atoms.

[0065] The cycloalkyl group represented by R3 and R4 is preferably a cycloalkyl group having 6 to 12 carbon atoms, more preferably a cycloalkyl group having 6 to 8 carbon atoms.

[0066] The cycloalkenyl group represented by R3 and R4 is, for example, preferably a cycloalkenyl group having 3 to 12 carbon atoms, more preferably a cycloalkenyl group having 6 to 8 carbon atoms.

[0067] The ring formed by bonding R3 and R4 to each other is a cyclic ketone structure, which may be a saturated cyclic ketone or an unsaturated cyclic ketone. This cyclic ketone is preferably a 6- to 10-membered ring, more preferably a 6- to 8-membered ring. R3 and R4 satisfy the relationship that the number of carbon atoms in the compound represented by formula II is 6 or more.

[0068] In formula III, R5 represents an alkyl group or a cycloalkyl group. 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. This alkyl group may have an ether bond in the chain, and may have a substituent such as a hydroxy group.

[0069] 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.

[0070] 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.

[0071] The alkyl group represented by R6 and R7 is, for example, preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms.

[0072] The cycloalkyl group represented by R6 and R7 is preferably a cycloalkyl group having 6 to 12 carbon atoms, more preferably a cycloalkyl group having 6 to 8 carbon atoms.

[0073] The ring formed by R6 and R7 bonding to each other is a cyclic ether structure, which is preferably a 4- to 8-membered ring, and more preferably a 5- to 7-membered ring.

[0074] R6 and R7 satisfy the relationship that the number of carbon atoms in the compound represented by formula IV is 6 or more.

[0075] In Formula V, R8 and R9 each independently represent an alkyl group or a cycloalkyl group, or are bonded to each other to form a ring, and L represents a single bond or an alkylene group.

[0076] The alkyl group represented by R8 and R9 is, for example, preferably an alkyl group having 6 to 12 carbon atoms, more preferably an alkyl group having 6 to 10 carbon atoms.

[0077] The cycloalkyl group represented by R8 and R9 is preferably a cycloalkyl group having 6 to 12 carbon atoms, more preferably a cycloalkyl group having 6 to 10 carbon atoms.

[0078] The ring formed by R8 and R9 bonding to each other is a cyclic diketone structure, which is preferably a 6- to 12-membered ring, and more preferably a 6- to 10-membered ring.

[0079] The alkylene group represented by L is, for example, preferably an alkylene group having 1 to 12 carbon atoms, and more preferably an alkylene group having 1 to 10 carbon atoms. R8, R9 and L satisfy the relationship that the compound represented by formula V has 6 or more carbon atoms. Specific examples of the compound (B) include the following compounds.

[0080] [ka]

[0081] In one embodiment, the treatment solution of the present invention contains Na, Ca, and Fe, and the content of each element is preferably in the range of 0.01 mass ppt to 1000 mass ppb. Na, Ca, and Fe are metal atoms that are mixed in during various processes leading up to the synthesis of the treatment solution of the present invention. When the concentration of each of these metal atoms is 1000 mass ppb or less, it is possible to prevent these metal atoms from remaining on the substrate as nuclei of residual components during treatment and causing defects.

[0082] On the other hand, while it is generally believed that the fewer these metal atoms there are, the better, it has been confirmed that defects tend to increase again when the concentration falls below 0.01 ppt by mass. Although the mechanism is unclear, it is presumed that when Na, Ca, or Fe is removed from the substrate, it is removed as a certain amount of atomic mass, entraining compound (B) and / or compound (C). Therefore, if there is too little Na, Ca, or Fe, the removal efficiency of compound (B) and / or compound (C) and Na, Ca, or Fe deteriorates, and they remain on the substrate, possibly causing defects.

[0083] The content of each of Na, Ca, and Fe atoms contained in the treatment liquid is more preferably 0.01 mass ppt to 500 mass ppb, and even more preferably 0.05 mass ppt to 100 mass ppb.

[0084] In one embodiment, the treatment liquid of the present invention preferably has a total content of metal particles of 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, as measured by SNP-ICP-MS (Single-Particle ICP-MS).

[0085] Metal atoms contained as impurities in semiconductor manufacturing processing solutions are one of the causes of defects in fine patterns and fine semiconductor elements. For this reason, it has been thought that the smaller the amount of metal atoms contained in semiconductor manufacturing processing solutions, the better. However, the present inventors have found that the amount of metal atoms contained in processing solutions does not necessarily correlate with the defect occurrence rate, and the defect occurrence rate varies.

[0086] Recently developed SNP-ICP-MS measurement has made it possible to measure the amount of metal atoms present in a solution separately as ionic metals and metal particles (non-ionic metals).Here, metal particles (non-ionic metals) are metal components that do not dissolve in the solution and exist as solids.

[0087] Until now, the amount of metal atoms contained in semiconductor manufacturing processing solutions has typically been analyzed using methods such as ICP-MS. However, conventional methods such as ICP-MS cannot distinguish between ionic metals derived from metal atoms and metal particles (non-ionic metals), so the amount is quantified as the total mass of metal atoms, i.e., the combined mass of ionic metals and particulate metals (non-ionic metals) (hereinafter also referred to as the "total metal amount").

[0088] The present inventors have conducted extensive research into the effects on defects of ionic metals derived from metal atoms contained in processing solutions and metal particles (non-ionic metals), which can now be identified and quantified using measurements using SNP-ICP-MS. As a result, they have found that the amount of metal particles (non-ionic metals) has a significant effect on the occurrence of defects, and that there is a correlation between the amount of metal particles (non-ionic metals) and the occurrence of defects.

[0089] In the treatment liquid of the present invention, the total content of metal particles as measured by SNP-ICP-MS is particularly preferably 1 to 50 mass ppt. Apparatuses that can be used for measurements using the SNP-ICP-MS method include the apparatus used in the examples described below (NexION350S, manufactured by PerkinElmer), as well as, for example, Agilent 8800 Triple Quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200), manufactured by Agilent Technologies; and Agilent 8900, manufactured by Agilent Technologies.

[0090] In the embodiment of the present invention, a mixture of two or more of the above-described treatment liquids of the present invention may be used as the treatment liquid of the present invention for various purposes.

[0091] <Production of processing fluids for semiconductor manufacturing, etc.> The treatment liquid of the present invention can be produced by a known method, for example, by synthesizing compound (A) by reacting raw materials in the presence of a catalyst to obtain a crude liquid containing compound (A), and then purifying this crude liquid by, for example, filtering as described below.

[0092] The catalyst can be appropriately selected depending on the compound (A), and examples thereof include sulfuric acid, HgSO, NaNH, Al(CH), IpcBH (Diisopinocampheylborane), solid catalysts containing copper oxide and zinc oxide, supported phosphoric acid catalysts, and supported copper catalysts.

[0093] In one embodiment of the method for producing a treatment liquid of the present invention, a compound containing at least one selected from Al, B, S, N, and K is preferably used as a catalyst, and in another embodiment, a compound containing at least one selected from Al, B, and S is preferably used as a catalyst.

[0094] The raw materials used in producing the treatment solution of the present invention are preferably purified in advance by distillation, ion exchange, filtration, or the like. For example, the purity is 99% by mass or more, preferably 99.9% by mass or more. It is more preferable to use high-purity grade raw materials, and it is particularly preferable to further purify them before use. Using such high-purity raw materials is important for achieving the remarkable effects of the present invention.

[0095] Furthermore, it is preferable that the catalyst used in the method for producing a treatment liquid of the present invention is purified in advance by distillation, ion exchange, filtration, etc. For example, a catalyst with a purity of 99% by mass or more, preferably 99.9% by mass or more, and a high-purity grade catalyst is preferred.

[0096] Next, a manufacturing apparatus that can be suitably used for manufacturing the treatment liquid of the present invention will be described.

[0097] [Manufacturing equipment] FIG. 1 is a schematic diagram illustrating one embodiment of a production apparatus that can be used in a method for producing a treatment liquid according to an embodiment of the present invention. The production apparatus 100 includes a tank 101, which includes a supply port 102 for supplying a cleaning liquid and / or an organic solvent (a crude liquid containing compound (A)) described below. The production apparatus 100 also includes a filtration device 105, which is connected to the tank 101 by a supply pipe 109, allowing fluids (such as cleaning liquid, organic solvent, and treatment liquid) to be transferred between the tank 101 and the filtration device 105. A valve 103 and a pump 104 are disposed in the supply pipe 109. In FIG. 1, the production apparatus 100 includes the tank 101 and the filtration device 105, but the production apparatus that can be used in a method for producing a treatment liquid according to an embodiment of the present invention is not limited to this.

[0098] In the manufacturing apparatus 100, a fluid supplied from a supply port 102 flows into a filtration device 105 via a valve 103 and a pump 104. The fluid discharged from the filtration device 105 passes through a circulation line 110 and is stored in a tank 101. The manufacturing apparatus 100 includes a discharge unit 111 that discharges the treatment liquid into a circulation pipeline 110. The discharge unit 1111 includes a valve 107 and a container 108, and the produced treatment liquid can be stored in the container 108 by switching between a valve 106 provided in the circulation pipeline and the valve 107. A switchable pipeline 113 is connected to the valve 107, and the cleaning liquid after circulating cleaning can be discharged to the outside of the manufacturing apparatus 100 via this pipeline 113. The cleaning liquid after circulating cleaning may contain particles, metal impurities, etc., and the manufacturing apparatus 100 that includes the pipeline 113 that discharges the cleaning liquid to the outside of the apparatus can produce a treatment liquid with better defect suppression performance without contaminating the filled portion of the container 108, etc.

[0099] Furthermore, the manufacturing apparatus 100 is provided with a cleaning liquid monitoring unit 112 in the circulation pipeline 110. In FIG. 1, the manufacturing apparatus 100 is provided with the cleaning liquid monitoring unit 112 in the circulation pipeline 110, but the manufacturing apparatus that can be used in the manufacturing method of the treatment liquid according to 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 may be provided in both the supply pipeline 109 and the circulation pipeline 110. Note that in the manufacturing apparatus 100, the cleaning liquid monitoring unit 112 is provided directly in the circulation pipeline 110, but the manufacturing apparatus that can be used in the manufacturing method of the treatment liquid according to the embodiment of the present invention is not limited to this. The cleaning liquid monitoring unit may be provided in a temporary storage tank (different from the tank 101) for the fluid (not shown) provided in the pipeline.

[0100] 2 is a schematic diagram showing another embodiment of a production apparatus that can be used in the production method of a treatment liquid according to an embodiment of the present invention. The production apparatus 200 includes a tank 101 and a filtration device 105, and further includes a distillation column 201 that is connected to the tank 101 via pipelines 202, 204, and 203 and that is arranged so that a fluid can be transferred between the tank 101 and the distillation column 201 via the pipelines. On the other hand, the production apparatus that can be used in the production method of a treatment liquid according to an embodiment of the present invention does not necessarily have to include the filtration device 105 and / or the distillation column 201, and may further include a reaction vessel or the like connected to the distillation column 201 via pipeline 203.

[0101] In manufacturing apparatus 200, a fluid supplied to distillation column 201 via pipe 203 is distilled in distillation column 201. The distilled fluid is stored in tank 101 via pipe 202. Supply pipe 109 is equipped with valves 103 and 206, and by switching this with valve 205 equipped in pipe 204, the fluid discharged from tank 101 can flow into filtration device 105. Furthermore, in manufacturing apparatus 200, the fluid discharged from tank 101 can also be allowed to flow again into distillation column 201. In this case, by switching valves 103, 206, and 205, the fluid flows from pipe 204 through valve 207 and pipe 203 into distillation column 201.

[0102] The material of the liquid-contacting part of the manufacturing equipment (the definition of the liquid-contacting part will be described later) is not particularly limited, but it is preferably formed from at least one selected from the group consisting of non-metallic materials and electropolished metallic materials, in that a treatment liquid with better defect suppression performance can be obtained. In this specification, the term "liquid-contacting part" refers to a part that may come into contact with a fluid (for example, the inner surface of a tank, a liquid-transfer pump, a damper, a packing, an O-ring, and the inner surface of a pipeline), and refers to a region 100 nm thick from the surface.

[0103] The non-metallic material is not particularly limited, but is preferably a polyethylene resin, a polypropylene resin, a polyethylene-polypropylene resin, or a fluorine-containing resin material, and is preferably a fluorine-containing resin material from the viewpoint of reducing the elution of metal atoms.

[0104] Examples of the fluorine-containing resin include perfluororesins, such as tetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), tetrafluoroethylene-ethylene copolymer resin (ETFE), trifluorochloroethylene-ethylene copolymer resin (ECTFE), polyvinylidene fluoride resin (PVDF), trifluorochloroethylene copolymer resin (PCTFE), and polyvinyl fluoride resin (PVF).

[0105] Particularly preferred fluorine-containing resins include tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-hexafluoropropylene copolymer resin.

[0106] The metal material is not particularly limited, and known materials can be used. The metal material may be, for example, a metal material having a total chromium and nickel content of more than 25 mass% relative to the total mass of the metal material, with a content of 30 mass% or more being more preferred. There is no particular upper limit to the total chromium and nickel content in the metal material, but it is generally preferred that the total content be 90 mass% or less. Examples of metal materials include stainless steel, carbon steel, alloy steel, nickel-chromium-molybdenum steel, chromium steel, chromium-molybdenum steel, manganese steel, and nickel-chromium alloy.

[0107] The stainless steel is not particularly limited, and known stainless steels can be used. Among them, an alloy containing 8% or more by mass of nickel is preferred, and an austenitic stainless steel containing 8% or more by mass of nickel is more preferred. Examples of austenitic stainless steel include SUS (Steel Use Stainless) 304 (Ni content 8% by mass, Cr content 18% by mass), SUS304L (Ni content 9% by mass, Cr content 18% by mass), SUS316 (Ni content 10% by mass, Cr content 16% by mass), and SUS316L (Ni content 12% by mass, Cr content 16% by mass).

[0108] The nickel-chromium alloy is not particularly limited, and any known nickel-chromium alloy can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75 mass % and a chromium content of 1 to 30 mass % is preferred.

[0109] Examples of nickel-chromium alloys include Hastelloy (trade name, the same applies hereinafter), Monel (trade name, the same applies hereinafter), and Inconel (trade name, the same applies hereinafter), etc. More specific examples include Hastelloy C-276 (Ni content 63 mass%, Cr content 16 mass%), Hastelloy-C (Ni content 60 mass%, Cr content 17 mass%), Hastelloy C-22 (Ni content 61 mass%, Cr content 22 mass%), etc. Furthermore, the nickel-chromium alloy may further contain boron, silicon, tungsten, molybdenum, copper, cobalt, and the like in addition to the above alloy, as required.

[0110] The method for electrolytically polishing a metal material is not particularly limited, and any known method can be used, such as those described in paragraphs 0011 to 0014 of JP 2015-227501 A and paragraphs 0036 to 0042 of JP 2008-264929 A.

[0111] It is presumed that the chromium content in the surface passive layer of a metal material becomes higher than the chromium content in the parent phase due to electrolytic polishing, and therefore, it is presumed that metal impurities containing metal atoms in an organic solvent are less likely to flow out of a distillation column whose liquid-contacting parts are formed from a metal material that has been electrolytically polished, and therefore, a distilled organic solvent with a reduced impurity content can be obtained. The metal material may be buffed. The buffing method is not particularly limited, and known methods can be used. The size of the abrasive grains used for the buffing finish is not particularly limited, but #400 or smaller is preferred, as this tends to reduce the surface irregularities of the metal material. The buffing is preferably performed before electrolytic polishing.

[0112] In order to obtain a treatment solution with better defect suppression performance, it is preferable that the liquid-contacting parts be made of electropolished stainless steel. In particular, when the manufacturing apparatus is equipped with a tank, it is more preferable that the liquid-contacting parts of the tank be made of electropolished stainless steel. The mass ratio of the Cr content to the Fe content in the liquid-contacting parts (hereinafter also referred to as "Cr / Fe") is not particularly limited, but is generally preferably 0.5 to 4. In particular, in order to make it more difficult for metal impurities and / or organic impurities to leach into the treatment solution, it is more preferable that it be greater than 0.5 and less than 3.5, and more preferably 0.7 or more and 3.0 or less. When the Cr / Fe ratio is greater than 0.5, metal leach-out from the tank can be suppressed, and when the Cr / Fe ratio is less than 3.5, peeling of the liquid-contacting parts, which can cause particles, is less likely to occur. The method for adjusting the Cr / Fe ratio in the above-mentioned metal material is not particularly limited, and examples thereof include a method for adjusting the content of Cr atoms in the metal material, and a method for making the chromium content in the passive layer of the polished surface greater than the chromium content in the parent phase by electrolytic polishing.

[0113] The metal material may be a metal material to which a coating technique has been applied. Coating technologies are broadly divided into three types: metallic coatings (various platings), inorganic coatings (various chemical conversion treatments, glass, concrete, ceramics, etc.), and organic coatings (rust-preventive oils, paints, rubber, plastics, etc.), but any of these is acceptable. Preferred coating techniques include surface treatment with rust preventative oils, rust inhibitors, corrosion inhibitors, chelating compounds, peelable plastics, and lining agents.

[0114] Among these, preferred coating techniques include surface treatments using corrosion inhibitors, chelating compounds, and lining agents. Examples of corrosion inhibitors include various chromates, nitrites, silicates, phosphates, carboxylic acids (oleic acid, dimer acid, naphthenic acid, etc.), carboxylic acid metal soaps, sulfonates, amine salts, and esters (glycerin esters and phosphate esters of higher fatty acids). Examples of chelating compounds include ethylenedianetetraacetic acid, gluconic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, and diethylenetriaminepentaacetic acid. Examples of lining agents include fluororesin lining agents. Treatments using phosphates or fluororesin lining agents are particularly preferred.

[0115] The manufacturing apparatus described above is more likely to produce a treatment liquid with better defect suppression performance by including the filtration device 105. The filtering member contained in the filtration device 105 is not particularly limited, but is preferably at least one selected from the group consisting of a filter with a particle removal diameter of 20 nm or less and a metal ion adsorption filter, and more preferably a filter with a particle removal diameter of 20 nm or less and a metal ion adsorption filter.

[0116] Filter with particle size of 20nm or less A filter with a particle removal diameter of 20 nm or less has the function of efficiently removing particles with a diameter of 20 nm or more from organic solvents and the like that are the raw materials for the processing liquid. The particle size of the filter is preferably 1 to 15 nm, more preferably 1 to 12 nm. If the particle size is 15 nm or less, finer particles can be removed, and if the particle size is 1 nm or more, the filtration efficiency is improved. Here, the particle size refers to the minimum size of particles that can be removed by the filter. For example, if the particle size of a filter is 20 nm, it can remove particles with a diameter of 20 nm or more.

[0117] Examples of filter materials include nylons such as 6-nylon and 6,6-nylon, polyethylene, polypropylene, polystyrene, polyimide, polyamideimide, and fluororesin. The polyimide and / or polyamideimide may have at least one selected from the group consisting of a carboxy group, a salt-type carboxy group, and an -NH- bond. Fluororesin, polyimide, and / or polyamideimide are excellent in solvent resistance. Furthermore, nylons such as 6-nylon and 6,6-nylon are particularly preferred from the viewpoint of adsorbing metal ions.

[0118] Filtration device 105 may contain a plurality of the above filters. When filtration device 105 contains a plurality of filters, the other filter is preferably, but not limited to, a filter with a particle removal diameter of 50 nm or more (for example, a microfiltration membrane for removing fine particles with a pore diameter of 50 nm or more). When fine particles are present in the product to be purified in addition to colloidal impurities, particularly colloidal impurities containing metal atoms such as iron or aluminum, filtering the product to be purified using a filter with a particle removal diameter of 50 nm or more (for example, a microfiltration membrane for removing fine particles with a pore diameter of 50 nm or more) before filtering using a filter with a particle removal diameter of 20 nm or less (for example, a microfiltration membrane with a pore diameter of 20 nm or less). This improves the filtration efficiency of the filter with a particle removal diameter of 20 nm or less (for example, a microfiltration membrane with a pore diameter of 20 nm or less), and further improves particle removal performance.

[0119] Metal ion adsorption filter The filtration device 105 preferably contains a metal ion adsorption filter. The metal ion adsorption filter is not particularly limited, and examples thereof include known metal ion adsorption filters.

[0120] Among these, an ion-exchangeable filter is preferred as the metal ion adsorption filter. Here, the metal ions to be adsorbed are not particularly limited, but are preferably ions of a metal containing one selected from the group consisting of Fe, Cr, Ni, and Pb, and more preferably ions of a metal containing each of Fe, Cr, Ni, and Pb, because they are likely to cause defects in semiconductor devices.

[0121] The metal ion adsorption filter preferably contains acid groups on its surface, such as sulfo groups and carboxy groups, in order to improve the metal ion adsorption performance.

[0122] Examples of the substrate (material) constituting the metal ion adsorption filter include cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, fluororesin, etc. From the viewpoint of efficiency in adsorbing metal ions, nylon is particularly preferable.

[0123] The metal ion adsorption filter may be made of a material containing polyimide and / or polyamideimide. Examples of the metal ion adsorption filter include the polyimide and / or polyamideimide porous membrane described in JP 2016-155121 A.

[0124] The polyimide and / or polyamideimide porous membrane may contain at least one selected from the group consisting of a carboxy group, a salt-type carboxy group, and an -NH- bond. When the metal ion adsorption filter is made of a fluororesin, a polyimide, and / or a polyamideimide, it has better solvent resistance.

[0125] Organic impurity adsorption filter The filtration device 105 may further include an organic impurity adsorption filter. The organic impurity adsorption filter is not particularly limited, and examples thereof include known organic impurity adsorption filters. In particular, it is preferable that the organic impurity adsorption filter has an organic skeleton on its surface that can interact with organic impurities (in other words, the surface is modified with an organic skeleton that can interact with organic impurities) in order to improve the adsorption performance of organic impurities. Examples of organic skeletons that can interact with organic impurities include chemical structures that can react with organic impurities and capture the organic impurities in the organic impurity adsorption filter. More specifically, when the organic impurities contain n-long-chain alkyl alcohol (a structural isomer when 1-long-chain alkyl alcohol is used as the organic solvent), the organic skeleton can be an alkyl group. Furthermore, when the organic impurities contain dibutylhydroxytoluene (BHT), the organic skeleton can be a phenyl group.

[0126] Examples of the substrate (material) that constitutes the organic impurity adsorption filter include activated carbon-supported cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, and fluororesin.

[0127] Furthermore, the organic impurity adsorption filter may also be a filter in which activated carbon is fixed to a nonwoven fabric, as described in JP-A-2002-273123 and JP-A-2013-150979.

[0128] As for the organic impurity adsorption filter, in addition to the chemical adsorption (adsorption using an organic impurity adsorption filter having an organic skeleton on the surface that can interact with organic impurities) described above, a physical adsorption method can also be applied.

[0129] For example, if BHT is included as an organic impurity, the structure of BHT is larger than 10 angstroms (=1 nm). Therefore, if an organic impurity adsorption filter with a pore size of 1 nm is used, BHT cannot pass through the pores of the filter. In other words, BHT is physically captured by the filter and removed from the product to be purified. In this way, organic impurities can be removed not only by chemical interaction but also by applying physical removal methods. However, in this case, a filter with a pore size of 3 nm or more is used as a "particle removal filter," and a filter with a pore size of less than 3 nm is used as an "organic impurity adsorption filter."

[0130] To reiterate, when using filters, different filters may be combined. In this case, filtering with the first filter may be performed only once or two or more times. When different filters are combined to perform filtering two or more times, the filters may be of the same type or different types, but it is preferable that they are different types. Typically, it is preferable that the first filter and the second filter differ in at least one of the pore size and constituent material.

[0131] It is preferable that the pore size of the second or subsequent filtering steps be the same or smaller than that of the first filtering step. It is also possible to combine first filters with different pore sizes within the above-mentioned range. The pore size here refers to the nominal value of the filter manufacturer. Commercially available filters can be selected from various filters provided by, for example, Nippon Pall Corporation, Advantec Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), or Kitz Microfilter Co., Ltd. Other examples that can be used include polyamide "P-Nylon Filter (pore size 0.02 μm, critical surface tension 77 mN / m)" (manufactured by Nippon Pall Corporation), high-density polyethylene "PE Clean Filter (pore size 0.02 μm)" (manufactured by Nippon Pall Corporation), and high-density polyethylene "PE Clean Filter (pore size 0.01 μm)" (manufactured by Nippon Pall Corporation).

[0132] The method for producing a processing liquid according to an embodiment of the present invention may include a step of cleaning a production apparatus using a cleaning liquid. In this method, the cleaning liquid is supplied from a supply port 102 of a tank 101. The amount of the cleaning liquid supplied is not particularly limited, but is preferably an amount sufficient to sufficiently clean the liquid-contacting parts of the tank 101, and the volume of the cleaning liquid supplied is preferably 30% by volume or more of the volume of the tank 101. When the cleaning liquid is supplied from the supply port 102, the valve 103 may be open or closed. However, it is preferable to close the valve 103 when the cleaning liquid is supplied from the supply port 102, as this makes it easier to clean the tank 101.

[0133] The cleaning liquid supplied to the tank 101 may be immediately transferred through the manufacturing equipment, or may be transferred through the manufacturing equipment (e.g., via the supply pipeline 109) after cleaning the inside of the tank 101. There are no particular limitations on the method for cleaning the inside of the tank 101 using the cleaning liquid, and examples of such methods include cleaning by rotating a stirring blade (not shown) provided in the tank 101. There are no particular limitations on the time for cleaning the tank using the cleaning liquid, and the time may be appropriately selected depending on the material of the liquid-contacting parts of the tank 101, the type of processing liquid being produced, the possibility of contamination, and other factors. Generally, a time period of approximately 0.1 seconds to 48 hours is preferable. When only the tank 101 is cleaned, the cleaning liquid after cleaning may be discharged, for example, from a discharge port (not shown) provided at the bottom of the tank.

[0134] The method for cleaning the supply pipeline 109 and the like of the manufacturing apparatus 100 with the cleaning liquid is not particularly limited, but a preferred method is to open the valves 103 and 106, close the valve 107, operate the pump 104, and circulate the cleaning liquid within the manufacturing apparatus through the supply pipeline 109 and the circulation pipeline 110 (hereinafter also referred to as "circulation cleaning"). By doing so, foreign matter and the like adhering to the liquid-contacting parts of the tank 101, the filtration device 105, the supply pipeline 109, and the like can be efficiently dispersed and / or more efficiently dissolved by the cleaning liquid while the cleaning liquid is being transferred.

[0135] In particular, when the manufacturing equipment is equipped with a filtration device, circulation cleaning is a more preferable cleaning method. An example of circulation cleaning will be explained using Figure 1. First, the cleaning liquid supplied from tank 101 through valve 103 into the manufacturing equipment passes through supply pipe 109 (through filtration device 105, circulation pipe 110, and valve 106) and returns (circulates) to tank 101 again. At this time, the cleaning liquid is filtered by filtration device 105, and particles dissolved and dispersed in the cleaning liquid are removed, thereby further improving the cleaning effect.

[0136] As another form of the cleaning method, for example, a method may be used in which valves 103 and 107 are opened, valve 106 is closed, pump 104 is operated, and the cleaning liquid supplied into the manufacturing apparatus from supply port 102 of tank 101 is caused to flow into filtration device 105 through valve 103 and pump 104, and then the cleaning liquid is discharged outside the manufacturing apparatus via valve 107 without being circulated (hereinafter this method is also referred to as "batch cleaning" in this specification). In this case, the cleaning liquid may be supplied into the manufacturing apparatus in a fixed amount intermittently as described above, or may be supplied into the manufacturing apparatus continuously.

[0137] (cleaning solution) The cleaning solution used in the above-described pre-cleaning is not particularly limited, and any known cleaning solution can be used.

[0138] Examples of the cleaning liquid include water, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

[0139] Furthermore, the cleaning liquid may be, for example, one described in JP-A-2016-57614, JP-A-2014-219664, JP-A-2016-138219, and JP-A-2015-135379.

[0140] The cleaning solutions used were PGME (propylene glycol monomethyl ether), CyPe (cyclopentanone), CyPn (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), and PEG (propylene glycol monomethyl ether acetate). Preferably, the solvent contains at least one selected from the group consisting of 4-methyl-2-pentanol (MEK), methyl ethyl ketone (MEK), and 4-methyl-2-pentanol (MIBC), more preferably contains at least one selected from the group consisting of PGMEA, NMP, PGME, nBA, PC, CyHx, GBL, MIBC, EL, DMSO, iAA, MEK, PC, and CyPe, and even more preferably consists of at least one selected from the group consisting of PGMEA, NMP, PGME, nBA, PC, CyHx, GBL, MIBC, EL, DMSO, iAA, MEK, PC, and CyPe.

[0141] The cleaning liquid may be used alone or in combination of two or more. The treatment liquid of the present invention may also be used as the cleaning liquid.

[0142] [Metal content adjustment method] In the treatment solution of the present invention, the ion concentrations of Cr, Co, Cu, Pb, Li, Mg, Mn, Ni, K, Ag, Zn, etc. are preferably 1 ppm (parts per million) or less, more preferably 1 ppb or less, and particularly preferably on the order of ppt (all concentrations are by mass), and particularly preferably substantially free of these ions.

[0143] The metal content in the treatment solution of the present invention may be adjusted by, for example, repeating distillation, filtration with a filter, filtration using an ion exchange resin, adsorption purification, or the like, and sufficiently purifying the treatment solution at least at one of the stages of the raw materials used in producing the treatment solution and the stage after the treatment solution has been prepared.

[0144] Here, the method for adjusting the metal content (hereinafter also referred to as a "method for reducing the metal concentration") is not particularly limited, but examples thereof include adsorption purification using silicon carbide, as described in International Publication No. WO12 / 043496, and further, examples of a method for sufficient purification that combines distillation, filtration with a filter, and filtration using an ion exchange resin are exemplified as preferred forms.

[0145] In order to obtain the effects of the present invention, it is particularly preferable that the metal content be adjusted at the stage of raw materials used in producing the treatment solution. Furthermore, it is preferable to use raw materials of a grade in which specific metal atoms, inorganic ions such as sulfate ions, chloride ions, and nitrate ions, and metal ions described below are reduced.

[0146] Other methods for reducing the metal concentration include using a container that minimizes the elution of impurities as a "container" for containing raw materials used in producing the treatment solution, as described below with respect to the container for containing the treatment solution of the present invention. Another method is to provide a fluororesin lining to the inner wall of "piping" during preparation of the treatment solution, so as to prevent elution of metal components from the "piping."

[0147] [Impurities and coarse particles] Furthermore, it is preferable that the treatment liquid of the present invention is substantially free of coarse particles. The coarse particles contained in the treatment liquid include particles such as dust, dirt, organic solids, and inorganic solids contained as impurities in the raw materials, and particles such as dust, dirt, organic solids, and inorganic solids introduced as contaminants during the preparation of the treatment liquid, and these particles ultimately remain as particles in the treatment liquid without dissolving. The amount of coarse particles present in the treatment liquid can be measured in the liquid phase using a commercially available measuring device that uses a laser as a light source for light scattering liquid particle measurement.

[0148] [Kit and concentrate] The treatment solution of the present invention may be prepared as a kit to which other raw materials are added separately. In this case, the other raw materials to be added separately at the time of use may be a solvent such as water or an organic solvent, or other compounds may be mixed depending on the application. From the viewpoint of significantly achieving the effects of the present invention, the solvent that can be used in this case should have a Na, Ca, or Fe content within the specific value range of the present invention described above, thereby significantly achieving the desired effects of the present invention.

[0149] <Container> The treatment solution of the present invention can be filled into any container (regardless of whether it is a kit) and stored, transported, and used, as long as corrosiveness and other factors are not an issue. A container with high cleanliness and low impurity elution is preferred for semiconductor applications. Usable containers include, but are not limited to, the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd.

[0150] The liquid-contacting portion of the container is preferably made of a non-metallic material or stainless steel. Examples of non-metallic materials include the materials exemplified as non-metallic materials used for the liquid-contacting parts of the distillation column described above. In particular, among the above, when a container having a liquid-contacting part made of a fluororesin is used, the occurrence of the problem of elution of ethylene or propylene oligomers can be suppressed compared to when a container having a liquid-contacting part made of a polyethylene resin, a polypropylene resin, or a polyethylene-polypropylene resin is used.

[0151] A specific example of such a container whose liquid-contacting part is made of a fluororesin is the FluoroPure PFA composite drum manufactured by Entegris, Inc. Containers described on page 4 or the like of JP-A-3-502677, page 3 or the like of WO 2004 / 016526, and pages 9 and 16 or the like of WO 99 / 46309 can also be used. When the liquid-contacting part is made of a non-metallic material, it is preferable that the elution into the non-metallic material is suppressed.

[0152] As for the container, the liquid-contacting part that comes into contact with the treatment liquid is preferably formed from stainless steel, and more preferably formed from electrolytically polished stainless steel.

[0153] When the treatment liquid is stored in the container, impurity metals and / or organic impurities are less likely to be eluted into the treatment liquid stored in the container.

[0154] The form of the stainless steel is as already explained as the material for the liquid-contacting parts of the distillation column. The same applies to electrolytically polished stainless steel.

[0155] The Cr / Fe ratio in the stainless steel forming the liquid-contacting portion of the container is the same as that already explained for the liquid-contacting portion of the tank.

[0156] It is preferable to wash the inside of these containers before filling. The liquid used for washing is not particularly limited, but it is preferable that the metal content be less than 0.001 parts per trillion by mass. Furthermore, depending on the application, the effects of the present invention can be significantly achieved by using water, as described below, or other organic solvents purified to have a metal content within the above range, or the treatment solution of the present invention itself, a diluted treatment solution of the present invention, or a liquid containing at least one of the compounds added to the treatment solution of the present invention.

[0157] After production, the treatment solution may be bottled in a container such as a gallon bottle or a coated bottle, and then transported and stored. The gallon bottle may be made of glass or other materials.

[0158] To prevent changes in the components of the solution during storage, the atmosphere inside the container may be replaced with an inert gas (such as nitrogen or argon) with a purity of 99.99995% by volume or higher. Gases with low water content are particularly preferred. The solution may be transported and stored at room temperature, but the temperature may be controlled to a range of -20°C to 30°C to prevent deterioration.

[0159] Furthermore, it is preferable to remove foreign matter adhering to the lids of various containers by washing them with an acid or organic solvent before washing the containers, in order to prevent contamination by foreign matter from the lids.

[0160] [water] The water used in connection with the present invention, such as water that can be used in the manufacturing process of the processing solution of the present invention, water that can be used in the pattern formation process of the present invention, water that can be used to clean the container containing the processing solution of the present invention, and water that can be used to measure the components of the processing solution of the present invention and evaluate the defect suppression performance and lithography performance related to the effects of the present invention, is preferably ultrapure water used in semiconductor manufacturing. It is also more preferable to use water that has been further purified to reduce inorganic anions, metal ions, etc. The purification method is not particularly limited, but purification using a filtration membrane or ion exchange membrane or purification by distillation is preferred. It is also preferable to perform purification using, for example, the method described in JP 2007-254168 A.

[0161] In one embodiment, the water preferably has a metal content of less than 0.001 parts per trillion (ppt) by weight.

[0162] [Clean room] It is preferable that all of the preparation of the processing solution of the present invention, handling including opening and / or cleaning of the container, filling of the processing solution, processing analysis, and measurement be performed in a clean room. The clean room preferably meets the 14644-1 clean room standard. It is preferable that the clean room meets any of ISO Class 1, ISO Class 2, ISO Class 3, and ISO Class 4, and it is more preferable that it meets ISO Class 1 or ISO Class 2, with ISO Class 1 being particularly preferable. [Uses of processing liquid] The processing solution of the present invention is preferably used in semiconductor manufacturing. Specifically, in the manufacturing process of semiconductor devices including lithography, etching, ion implantation, and stripping, the processing solution is used to treat organic materials after each step or before moving to the next step, and is preferably used as a prewet solution, developer, rinse, stripper, etc. For example, the processing solution can also be used to rinse the edge of a semiconductor substrate before and after resist coating.

[0163] The processing liquid can also be used as a cleaning liquid for equipment for producing various processing liquids used in semiconductor manufacturing.

[0164] The treatment liquid can also be used as a diluent for a resin contained in a resist liquid (described later), i.e., as a solvent contained in an actinic ray-sensitive or radiation-sensitive composition. Furthermore, the above-mentioned processing liquid can be suitably used for applications other than semiconductor manufacturing, and can also be used as a developer for polyimide, sensor resist, lens resist, etc., and a rinse liquid, etc.

[0165] The treatment liquid can also be used as a solvent for medical or cleaning purposes, and is particularly suitable for cleaning containers, pipes, and substrates (e.g., wafers and glass). <Pattern formation method> The treatment liquid of the present invention is basically a treatment liquid used as a developer, rinse, pre-wet liquid, stripper, etc. in a method for manufacturing a semiconductor device, and in one aspect, it is preferably used as a developer, rinse, or pre-wet liquid in a pattern formation method included in a method for manufacturing a semiconductor device.

[0166] The pattern formation method of the present invention includes a resist film formation step of applying an actinic ray- or radiation-sensitive composition (hereinafter also referred to as a "resist composition") to 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 resist film to light, and a treatment step of treating the substrate before being coated with the resist composition or the exposed resist film with the treatment liquid described above.

[0167] In the pattern formation method of the present invention, the treatment liquid of the present invention may be used as any one of a developer, a rinse liquid, and a prewet liquid, and is preferably used as any two of a developer, a rinse liquid, and a prewet liquid, and more preferably used as a developer, a rinse liquid, and a prewet liquid.

[0168] Each step included in the pattern forming method of the present invention will be described below. As examples of the treatment steps using the treatment liquid of the present invention, a prewetting step, a developing step, and a rinsing step will be described.

[0169] <Pre-wetting process> The pattern forming method of the present invention may include a prewetting step of applying a prewetting liquid to a substrate in advance to improve coatability before the step of forming a resist film using an actinic ray-sensitive or radiation-sensitive composition. For example, the prewetting step is described in JP 2014-220301 A, and these are incorporated herein by reference.

[0170] <Resist film formation process> 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 carried out by, for example, the following method.

[0171] To form a resist film (actinic ray-sensitive or radiation-sensitive composition film) on a substrate using the actinic ray-sensitive or radiation-sensitive composition, the components described below are dissolved in a solvent to prepare an actinic ray-sensitive or radiation-sensitive composition, which is then filtered through a filter as needed and applied to the substrate. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon and has a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less.

[0172] The actinic ray- or radiation-sensitive composition is applied by a suitable application method such as a spinner onto a substrate (e.g., silicon, silicon dioxide-coated) such as those used in the manufacture of integrated circuit devices. The composition is then dried to form a resist film. If necessary, various undercoating films (inorganic film, organic film, anti-reflective film) may be formed below the resist film.

[0173] The drying method generally used is drying by heating. Heating can be carried out by means of a conventional exposure / development machine, or by using a hot plate or the like.

[0174] The heating temperature is preferably 80 to 180° C., more preferably 80 to 150° C., even more 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 even more preferably 60 to 600 seconds.

[0175] The thickness of the resist film is generally 200 nm or less, and preferably 100 nm or less. For example, to resolve a 1:1 line and space pattern of 30 nm or less, the thickness of the resist film formed is preferably 50 nm or less. If the thickness is 50 nm or less, pattern collapse is less likely to occur when the developing step described below is applied, and better resolution performance can be obtained.

[0176] The film thickness is more preferably in the range of 15 nm to 45 nm. If the film thickness is 15 nm or more, sufficient etching resistance can be obtained. The film thickness is even more preferably in the range of 15 nm to 40 nm. If the film thickness is in this range, etching resistance and better resolution performance can be simultaneously satisfied.

[0177] In the pattern forming method of the present invention, an upper layer film (top coat film) may be formed on the resist film. The upper layer film can be formed using a composition for forming an upper layer film containing, for example, a hydrophobic resin, an acid generator, and a basic compound. The upper layer film and the composition for forming an upper layer film are described below.

[0178] <Exposure process> The exposure step is a step of exposing the resist film to light, and can be carried out, for example, by the following method. 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, writing without using a mask (direct writing) is common.

[0179] The actinic ray or radiation is not particularly limited, and examples thereof include KrF excimer laser, ArF excimer laser, EUV (Extreme Ultra Violet), electron beam (EB), etc. The exposure may be immersion exposure.

[0180] <Bake> In the pattern forming method of the present invention, it is preferable to perform baking (heating) after exposure and before development, as this promotes the reaction of the exposed areas and improves the sensitivity and pattern shape. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably from 30 to 1000 seconds, more preferably from 60 to 800 seconds, and even more preferably from 60 to 600 seconds. Heating can be carried out by means of a conventional exposure / development machine, and may also be carried out using a hot plate or the like.

[0181] <Developing process> The developing step is a step of developing the exposed resist film with a developer.

[0182] As development methods, for example, a method of immersing a substrate in a tank filled with developer for a certain period of time (dip method), a method of developing by piling up developer on the surface of the substrate using surface tension and leaving it to stand for a certain period of time (puddle method), a method of spraying developer onto the surface of the substrate (spray method), and a method of continuously discharging developer while scanning a developer discharge nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispense method) can be applied. After the development step, a step of stopping the development while replacing the solvent with another solvent may be carried out.

[0183] The development time is not particularly limited as long as it is long enough to dissolve the resin in the unexposed areas, and is usually 10 to 300 seconds, preferably 20 to 120 seconds. The temperature of the developer is preferably from 0 to 50°C, more preferably from 15 to 35°C. The developing solution used in the developing step is preferably the processing solution described above. The developing solution is as described above. In addition to development using the processing solution, development using an alkaline developer may also be carried out (so-called double development).

[0184] <Rinse process> The rinsing step is a step of cleaning (rinsing) the developed wafer with a rinse liquid after the developing step. In the rinsing step, the developed wafer is cleaned with the rinse liquid.

[0185] The cleaning method is not particularly limited, and examples that can be used include a method in which a rinse solution is continuously discharged onto a substrate rotating at a constant speed (rotary discharge method), a method in which a substrate is immersed for a certain period of time in a tank filled with a rinse solution (dip method), and a method in which a rinse solution is sprayed onto the surface of the substrate (spray method). Among these, it is preferable to perform the cleaning method using the rotary discharge method, and then rotate the substrate at a rotation speed of 2000 rpm to 4000 rpm after cleaning to remove the rinse solution from the substrate.

[0186] There are no particular restrictions on the rinsing time, but it is usually 10 to 300 seconds, preferably 10 to 180 seconds, and most preferably 20 to 120 seconds. The temperature of the rinse liquid is preferably 0 to 50°C, more preferably 15 to 35°C. After the development process or the rinsing process, the developer or rinsing liquid adhering to the pattern can be removed using a supercritical fluid.

[0187] Furthermore, after the development treatment, rinsing treatment, or treatment with a supercritical fluid, a heat treatment can be performed to remove any solvent remaining in the pattern. The heating temperature is not particularly limited as long as a good resist pattern is obtained, and is usually 40 to 160°C. The heating temperature is preferably 50 to 150°C, and most preferably 50 to 110°C. The heating time is not particularly limited as long as a good resist pattern is obtained, but is usually 15 to 300 seconds, and preferably 15 to 180 seconds.

[0188] As the rinse liquid, it is preferable to use the above-mentioned treatment liquid, which has been described above.

[0189] As described above, in the pattern formation method of the present invention, any one of the developer, rinse liquid, and prewet liquid may be the treatment liquid of the present invention described above, but any two of the developer, rinse liquid, and prewet liquid may be the treatment liquid of the present invention, or all three of the developer, rinse liquid, and prewet liquid may be the treatment liquid of the present invention.

[0190] In one embodiment, the treatment liquid and the actinic ray-sensitive or radiation-sensitive resin composition used in the pattern formation method of the present invention preferably satisfy the following relationship. That is, it is preferable to use an actinic ray-sensitive or radiation-sensitive resin composition and the treatment liquid of the present invention that satisfy the relationship that the dissolution rate of an actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition in the treatment liquid of the present invention is 0.0016 to 0.33 nm / second.

[0191] Here, the dissolution rate of the actinic ray-sensitive or radiation-sensitive film in the processing liquid of the present invention refers to the rate at which the film thickness decreases when the formed actinic ray-sensitive or radiation-sensitive film is immersed in the processing liquid of the present invention, and in the present invention, this is the dissolution rate at 23° C. This dissolution rate is more preferably 0.0016 to 0.16 nm / sec, and even more preferably 0.0016 to 0.08 nm / sec.

[0192] <Actinic ray- or radiation-sensitive composition (resist composition)> Next, the actinic ray-sensitive or radiation-sensitive composition that is preferably used in combination with the processing solution of the present invention will be described in detail.

[0193] (A) Resin The actinic ray- or radiation-sensitive composition, which is preferably used in combination with the treatment liquid of the present invention, preferably contains a resin (A). The resin (A) has at least (i) a repeating unit having a group that decomposes under the action of an acid to generate a carboxyl group (which may further have a repeating unit having a phenolic hydroxyl group), or at least (ii) a repeating unit having a phenolic hydroxyl group.

[0194] When the compound has a repeating unit that is decomposed by the action of an acid to have a carboxyl group, the solubility in an alkaline developer increases and the solubility in an organic solvent decreases due to the action of an acid.

[0195] Examples of the repeating unit having a phenolic hydroxyl group contained in the resin (A) include a repeating unit represented by the following general formula (I).

[0196] [ka]

[0197] During the ceremony, 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 may be bonded to Ar4 to form a ring, in which case R 42 represents a single bond or an alkylene group. X4 is a single bond, -COO-, or -CONR 64 - represents R 64 represents a hydrogen atom or an alkyl group. L4 represents a single bond or an alkylene group. Ar4 represents an (n+1)-valent aromatic ring group, R 42 When it combines with the group to form a ring, it represents an (n+2)-valent aromatic ring group. n represents an integer of 1 to 5.

[0198] R in general formula (I) 41 , R 42 , R 43 The alkyl group is preferably an alkyl group having 20 or less carbon atoms, such as a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, or dodecyl group, 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.

[0199] R in general formula (I) 41 , R 42 , R 43The cycloalkyl group may be monocyclic or polycyclic, and preferred examples include monocyclic cycloalkyl groups having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.

[0200] R in general formula (I) 41 , R 42 , R 43 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom being particularly preferred.

[0201] R in general formula (I) 41 , R 42 , R 43 The alkyl group contained in the alkoxycarbonyl group of the above R 41 , R 42 , R 43 The same alkyl groups as those in the above are preferred.

[0202] Preferred examples of the substituent in each of the above groups include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amido group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group, and the number of carbon atoms of the substituent is preferably 8 or less.

[0203] 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 thereof include arylene groups having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, or an anthracenylene group, or aromatic ring groups containing a heterocycle, such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, or thiazole.

[0204] When n is an integer of 2 or greater, specific examples of the (n+1)-valent aromatic ring group are preferably groups obtained by removing any (n-1) hydrogen atoms from the above-mentioned specific examples of the divalent aromatic ring group. The (n+1)-valent aromatic ring group may further have a substituent.

[0205] Examples of the substituent that the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n+1)-valent aromatic ring group may have include, for example, R 41 , R 42 , R 43 Examples of the alkyl groups mentioned above, alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy groups, and aryl groups such as phenyl groups.

[0206] -CONR represented by X4 64 -(R 64 represents a hydrogen atom or an alkyl group) 64 The alkyl group is preferably an alkyl group having 20 or less carbon atoms, such as a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, or dodecyl group, which may have a substituent, and more preferably an alkyl group having 8 or less carbon atoms. X4 is preferably a single bond, -COO- or -CONH-, more preferably a single bond or -COO-.

[0207] The alkylene group in L4 preferably includes those having 1 to 8 carbon atoms, such as methylene, ethylene, propylene, butylene, hexylene, and octylene groups, which may have a substituent.

[0208] Ar4 is more preferably an aromatic ring group having 6 to 18 carbon atoms which may have a substituent, and particularly preferably a benzene ring group, a naphthalene ring group, or a biphenylene ring group.

[0209] The repeating unit represented by general formula (I) preferably has a hydroxystyrene structure, that is, Ar4 is preferably a benzene ring group.

[0210] The repeating unit having a phenolic hydroxyl group contained in the resin (A) is preferably a repeating unit represented by the following general formula (p1).

[0211] [ka]

[0212] In general formula (p1), R represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. Multiple Rs may be the same or different. R in general formula (p1) is particularly preferably a hydrogen atom.

[0213] In general formula (p1), Ar represents an aromatic ring, and examples thereof include aromatic hydrocarbon rings having 6 to 18 carbon atoms, such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, and a phenanthrene ring, which may have a substituent, and aromatic heterocycles containing heterocycles, 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, and a thiazole ring. Of these, a benzene ring is most preferred.

[0214] In the general formula (p1), m represents an integer of 1 to 5, and is preferably 1.

[0215] Specific examples of repeating units having a phenolic hydroxyl group contained in the resin (A) are shown below, but the present invention is not limited to these. In the formula, a represents 1 or 2.

[0216] [ka]

[0217] [ka]

[0218] [ka]

[0219] The content of repeating units having a phenolic hydroxyl group is preferably from 0 to 50 mol %, more preferably from 0 to 45 mol %, and even more preferably from 0 to 40 mol %, based on all repeating units in the resin (A).

[0220] The repeating unit of the resin (A) having a group that decomposes under the action of an acid to produce a carboxyl group is a repeating unit having a group in which the hydrogen atom of the carboxyl group is substituted with a group that decomposes and leaves under the action of an acid.

[0221] Examples of the group that can be eliminated by an acid include -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), -C(R 01 )(R 02 )(OR 39 ) etc.

[0222] In the formula, R 36 ~R 39 R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 36 and R 37 may be bonded to each other to form a ring.

[0223] 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.

[0224] The repeating unit contained in the resin (A) and having a group that decomposes under the action of an acid to generate a carboxyl group is preferably a repeating unit represented by the following general formula (AI).

[0225] [ka]

[0226] In general formula (AI), Xa1 represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group.

[0227] Rx1 to Rx3 each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. Two of Rx1 to Rx3 may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

[0228] The alkyl group represented by Xa1, which may have a substituent, is, for example, a methyl group or -CH2-R 11 Examples of such groups include groups represented by R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and 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, a hydroxymethyl group, or the like.

[0229] Examples of the divalent linking group for T include an alkylene group, a -COO-Rt- group, and a -O-Rt- group, in which Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0230] The alkyl group of Rx1 to Rx3 is preferably one having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group.

[0231] The cycloalkyl group represented by Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group.

[0232] The cycloalkyl group formed by combining two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, etc. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferred.

[0233] In the cycloalkyl group formed by combining two of Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group.

[0234] In the repeating unit represented by general formula (AI), for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0235] 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, and an alkoxycarbonyl group (having 2 to 6 carbon atoms), and the number of carbon atoms is preferably 8 or less.

[0236] The repeating unit represented by general formula (AI) is preferably an acid-decomposable (meth)acrylic acid tertiary alkyl ester repeating unit (a repeating unit in which Xa1 represents a hydrogen atom or a methyl group and T represents a single bond). More preferably, Rx1 to Rx3 each independently represent a linear or branched alkyl group, and even more preferably, Rx1 to Rx3 each independently represent a linear alkyl group.

[0237] Specific examples of the repeating unit contained in the resin (A) that has a group that decomposes under the action of an acid to generate a carboxyl group are shown below, but the present invention is not limited to these.

[0238] In the specific examples, Rx and Xa1 represent a hydrogen atom, CH3, CF3, or CH2OH. Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when a plurality of Zs are present, each is independent. p represents 0 or a positive integer. Examples of the substituent containing a polar group represented by Z include a linear or branched alkyl group or cycloalkyl group having a hydroxyl group, a cyano group, an amino group, an alkylamide group, or a sulfonamide group, and preferably an alkyl group having a hydroxyl group. As the branched alkyl group, an isopropyl group is particularly preferred.

[0239] [ka]

[0240] The content of repeating units having a group that decomposes under the action of an acid to generate a carboxyl group is preferably 15 to 90 mol%, more preferably 20 to 90 mol%, even more preferably 25 to 80 mol%, and even more preferably 30 to 70 mol%, based on all repeating units in the resin (A).

[0241] The resin (A) preferably further contains a repeating unit having a lactone group.

[0242] Any group containing a lactone structure can be used as the lactone group, but a group containing a 5- to 7-membered ring lactone structure is preferred, and a group in which another ring structure is condensed with the 5- to 7-membered ring lactone structure in the form of a bicyclo structure or a spiro structure is preferred.

[0243] It is more preferable that the compound has a repeating unit having a group with a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-16). The group with a lactone structure may be directly bonded to the main chain. Preferred lactone structures are groups represented by general formulas (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14).

[0244] [ka]

[0245] The lactone structure portion may or may not have a substituent (Rb2). Preferred examples of the substituent (Rb2) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or greater, multiple Rb2 may be the same or different, and multiple Rb2 may be bonded to form a ring.

[0246] Examples of the repeating unit having a group with a lactone structure represented by any of general formulae (LC1-1) to (LC1-16) include a repeating unit represented by the following general formula (AII).

[0247] [ka]

[0248] In general formula (AII), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group of Rb0 may have include a hydroxyl group and a halogen atom. 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. 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 combining these. A single bond or a linking group represented by -Ab1-CO2- is preferred. Ab1 represents a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group. V represents a group represented by any one of general formulas (LC1-1) to (LC1-16).

[0249] A repeating unit having a group with a lactone structure usually has optical isomers, and any of the optical isomers may be used. One optical isomer may be used alone, or multiple optical isomers may be used in combination. When one optical isomer is primarily used, the optical purity (ee) is preferably 90 or more, more preferably 95 or more.

[0250] Specific examples of repeating units having a group with a lactone structure are listed below, but the present invention is not limited to these.

[0251] [ka]

[0252] [ka]

[0253] The content of the repeating unit having a lactone group is preferably 1 to 65 mol %, more preferably 1 to 30 mol %, even more preferably 5 to 25 mol %, and even more preferably 5 to 20 mol %, based on all repeating units in the resin (A).

[0254] The resin (A) may further have 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. This improves substrate adhesion and developer affinity. The alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group, a diamantyl group, or a norbornane group. The polar group is preferably a hydroxyl group or a cyano group.

[0255] Specific examples of repeating units having a polar group are listed below, but the present invention is not limited to these.

[0256] [ka]

[0257] When the resin (A) has a repeating unit containing an organic group having a polar group, the content thereof is preferably 1 to 50 mol %, more preferably 1 to 30 mol %, even more preferably 5 to 25 mol %, and still more preferably 5 to 20 mol %, based on the total repeating units in the resin (A).

[0258] Furthermore, the repeating unit may contain a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (photoacid-generating group). In this case, the repeating unit having the photoacid-generating group can be considered to correspond to the compound (B) that generates an acid upon irradiation with actinic rays or radiation, which will be described later. An example of such a repeating unit is a repeating unit represented by the following general formula (4).

[0259] [ka]

[0260] R 41 represents a hydrogen atom or a methyl group. 41 represents a single bond or a divalent linking group. 42 represents a divalent linking group. W represents a structural moiety that is decomposed by irradiation with actinic rays or radiation to generate an acid in the side chain. Specific examples of the repeating unit represented by formula (4) are shown below, but the present invention is not limited to these.

[0261] [ka]

[0262] Other examples of the repeating unit represented by general formula (4) include the repeating units described in paragraphs

[0094] to

[0105] of JP-A No. 2014-041327.

[0263] 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 even more preferably 5 to 30 mol %, based on the total repeating units in the resin (A).

[0264] Resin (A) can be synthesized by a conventional method (e.g., radical polymerization). For example, typical synthesis methods include bulk polymerization, in which a monomer species and an initiator are dissolved in a solvent and polymerized by heating, and dropwise polymerization, in which a solution of a monomer species and an initiator is added dropwise to a heated solvent over 1 to 10 hours, with dropwise polymerization being preferred.

[0265] Examples of reaction solvents 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; and solvents that dissolve the actinic ray-sensitive or radiation-sensitive composition, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone, which will be described later. It is more preferable to carry out the polymerization using the same solvent as that used in the actinic ray-sensitive or radiation-sensitive composition. This can suppress the generation of particles during storage.

[0266] The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. The polymerization is initiated using a commercially available radical initiator (e.g., azo initiator, peroxide, etc.). Azo initiators are preferred as the radical initiator, and azo initiators having an ester group, cyano group, or carboxyl group are preferred. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, and dimethyl 2,2'-azobis(2-methylpropionate). If desired, the initiator is added additionally or in portions. After the reaction is complete, the desired polymer is recovered by adding the mixture to a solvent and recovering the powder or solid form. The concentration of the reaction mixture is 5 to 50% by mass, preferably 10 to 30% by mass.

[0267] The reaction temperature is usually 10 to 150°C, preferably 30 to 120°C, and more preferably 60 to 100°C.

[0268] For purification, conventional methods can be applied, such as a liquid-liquid extraction method in which residual monomers and oligomer components are removed by washing with water or by combining an appropriate solvent; a purification method in a solution state, such as ultrafiltration in which only those having a specific molecular weight or less are extracted and removed; a reprecipitation method in which a resin solution is dropped into a poor solvent to solidify the resin in the poor solvent, thereby removing residual monomers, etc.; and a purification method in a solid state, such as washing the filtered resin slurry with a poor solvent.

[0269] The weight-average molecular weight of resin (A), as determined by the GPC method and converted into polystyrene, is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and most preferably 5,000 to 15,000. By setting the weight-average molecular weight to 1,000 to 200,000, deterioration in heat resistance and dry etching resistance can be prevented, and deterioration in developability and deterioration in film-formability due to increased viscosity can be prevented.

[0270] Another particularly preferred embodiment of the weight average molecular weight of resin (A) is 3,000 to 9,500 in terms of polystyrene as determined by the GPC method. By setting the weight average molecular weight to 3,000 to 9,500, resist residue (hereinafter also referred to as "scum") is particularly suppressed, allowing for the formation of better patterns.

[0271] The dispersity (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 dispersity, the better the resolution and resist shape, and the smoother the sidewalls of the resist pattern, resulting in excellent roughness.

[0272] In the actinic ray-sensitive or radiation-sensitive composition, the content of the resin (A) is preferably from 50 to 99.9 mass % of the total solid content, and more preferably from 60 to 99.0 mass %.

[0273] In the actinic ray-sensitive or radiation-sensitive composition, the resin (A) may be used alone or in combination.

[0274] The resin (A) may also contain a repeating unit represented by the following general formula (VI).

[0275] [ka]

[0276] In general formula (VI), R61 , 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 may be bonded to Ar6 to form a ring, in which case R 62 represents a single bond or an alkylene group. X6 is a single bond, -COO-, or -CONR 64 - represents R 64 represents a hydrogen atom or an alkyl group. L6 represents a single bond or an alkylene group. Ar6 represents an (n+1)-valent aromatic ring group, R 62 When it combines with the group to form a ring, it represents an (n+2)-valent aromatic ring group. When n≧2, each Y2 independently represents a hydrogen atom or a group which is eliminated by the action of an acid, provided that at least one Y2 represents a group which is eliminated by the action of an acid. n represents an integer of 1 to 4.

[0277] As the group Y2 that is eliminated by the action of an acid, a structure represented by the following general formula (VI-A) is more preferable.

[0278] [ka]

[0279] 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. M represents a single bond or a divalent linking group. Q represents an alkyl group, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, or an aldehyde group. At least two of Q, M and L1 may be bonded to form a ring (preferably a 5- or 6-membered ring).

[0280] The repeating unit represented by the above general formula (VI) is preferably a repeating unit represented by the following general formula (3).

[0281] [ka]

[0282] In general formula (3), Ar3 represents an aromatic ring group.

[0283] 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 heterocyclic group. M3 represents a single bond or a divalent linking group. Q3 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. At least two of Q3, M3 and R3 may be bonded to form a ring. The aromatic ring group represented by Ar3 is the same as Ar6 in the above general formula (VI) when n is 1, more preferably a phenylene group or a naphthylene group, and even more preferably a phenylene group.

[0284] Specific examples of the repeating unit represented by formula (VI) are shown below, but the present invention is not limited to these.

[0285] [ka]

[0286] [ka]

[0287] It is also preferable that the resin (A) contains a repeating unit represented by the following general formula (4).

[0288] [ka]

[0289] In general formula (4), 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 may be bonded to L4 to form a ring, in which case R 42 represents an alkylene group.

[0290] L4 represents a single bond or a divalent linking group, R 42 When it forms a ring with , it represents a trivalent linking group. R 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 heterocyclic group. M4 represents a single bond or a divalent linking group. Q4 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. Q4, M4 and R 44 At least two of these may be bonded to form a ring. R 41 , R 42 and R 43 represents R in the general formula (V) 51 , R 52 , R 53 The same applies to the preferred ranges. L4 has the same meaning as L5 in the general formula (V) above, and the preferred range is also the same.

[0291] R 44 and R 45 has the same meaning as R3 in the above general formula (3), and the preferred range is also the same. M4 has the same meaning as M3 in the general formula (3) above, and the preferred range is also the same. Q4 has the same meaning as Q3 in the general formula (3) above, and the preferred range is also the same. Q4, M4 and R 44Examples of the ring formed by combining at least two of the above include a ring formed by combining at least two of Q3, M3 and R3, and the preferred ranges are also the same.

[0292] Specific examples of the repeating unit represented by formula (4) are shown below, but the present invention is not limited to these.

[0293] [ka]

[0294] The resin (A) may also contain a repeating unit represented by the following general formula (BZ).

[0295] [ka]

[0296] In 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.

[0297] R1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkyloxycarbonyl group. Specific examples of the repeating unit represented by general formula (BZ) are shown below, but the invention is not limited to these.

[0298] [ka]

[0299] [ka]

[0300] The repeating unit having an acid-decomposable group may be of one type, or two or more types may be used in combination.

[0301] The content of repeating units having an acid-decomposable group in the resin (A) (the total content when multiple types are contained) is preferably 5 mol % or more and 80 mol % or less, more preferably 5 mol % or more and 75 mol % or less, and even more preferably 10 mol % or more and 65 mol % or less, based on the total repeating units in the resin (A).

[0302] The resin (A) may contain a repeating unit represented by the following general formula (V) or (VI).

[0303] [ka]

[0304] During the ceremony, R6 and R7 each independently represent a hydrogen atom, a hydroxy 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. n3 represents an integer of 0 to 6. n4 represents an integer of 0 to 4. X 4 is a methylene group, an oxygen atom or a sulfur atom.

[0305] Specific examples of the repeating unit represented by formula (V) or (VI) are shown below, but are not limited to these.

[0306] [ka]

[0307] Resin (A) may further contain a repeating unit having a silicon atom in the side chain. Examples of repeating units having a silicon atom in the side chain include (meth)acrylate repeating units having a silicon atom and vinyl repeating units having a silicon atom. The repeating unit having a silicon atom in the side chain is typically a repeating unit having a group having a silicon atom in the side chain. Examples of the group having a silicon atom include trimethylsilyl, triethylsilyl, triphenylsilyl, tricyclohexylsilyl, tristrimethylsiloxysilyl, tristrimethylsilylsilyl, methylbistrimethylsilylsilyl, methylbistrimethylsiloxysilyl, dimethyltrimethylsilylsilyl, dimethyltrimethylsiloxysilyl, or cyclic or linear polysiloxanes such as those shown below, or cage, ladder, or random silsesquioxane structures. In the formula, R and R each independently represent a monovalent substituent. * represents a bond.

[0308] [ka]

[0309] Suitable examples of the repeating unit having the above group include a repeating unit derived from an acrylate or methacrylate compound having the above group, and a repeating unit derived from a compound having the above group and a vinyl group.

[0310] The repeating unit having a silicon atom is preferably a repeating unit having a silsesquioxane structure, which enables the development of extremely excellent collapse performance in the formation of a pattern that is ultrafine (for example, a line width of 50 nm or less) and has a cross-sectional shape with a high aspect ratio (for example, film thickness / line width of 3 or more).

[0311] Examples of the silsesquioxane structure include a cage silsesquioxane structure, a ladder silsesquioxane structure, a random silsesquioxane structure, etc. Among these, the cage silsesquioxane structure is preferred.

[0312] Here, the cage silsesquioxane structure refers to a silsesquioxane structure having a cage skeleton. The cage silsesquioxane structure may be a complete cage silsesquioxane structure or an incomplete cage silsesquioxane structure, but is preferably a complete cage silsesquioxane structure.

[0313] The ladder-type silsesquioxane structure is a silsesquioxane structure having a ladder-like skeleton. The random silsesquioxane structure is a silsesquioxane structure whose skeleton is random.

[0314] The cage silsesquioxane structure is preferably a siloxane structure represented by the following formula (S).

[0315] [ka]

[0316] In the above formula (S), R represents a monovalent organic group, and multiple Rs may be the same or different.

[0317] The organic group is not particularly limited, and specific examples include a hydroxy group, a nitro group, a carboxy group, an alkoxy group, an amino group, a mercapto group, a blocked mercapto group (for example, a mercapto group blocked (protected) with an acyl group), an acyl group, an imido group, a phosphino group, a phosphinyl group, a silyl group, a vinyl group, a hydrocarbon group which may have a heteroatom, a (meth)acrylic group-containing group, and an epoxy group-containing group.

[0318] Examples of the heteroatom of the hydrocarbon group which may have a heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom.

[0319] Examples of the hydrocarbon group of the hydrocarbon group which may have a hetero atom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group formed by combining these groups.

[0320] The aliphatic hydrocarbon group may be linear, branched, or cyclic. Specific examples of the aliphatic hydrocarbon group include linear or branched alkyl groups (particularly having 1 to 30 carbon atoms), linear or branched alkenyl groups (particularly having 2 to 30 carbon atoms), and linear or branched alkynyl groups (particularly having 2 to 30 carbon atoms).

[0321] Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 18 carbon atoms, such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

[0322] When the resin (A) has 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 the total repeating units in the resin (A).

[0323] (B) A compound that generates an acid when exposed to actinic rays or radiation (a photoacid generator) The actinic ray-sensitive or radiation-sensitive resin composition preferably contains a compound that generates an acid when exposed to actinic rays or radiation (hereinafter also referred to as a "photo acid generator (PAG)").

[0324] The photoacid generator may be in the form of a low molecular weight compound, or may be incorporated into a part of a polymer, or may be in the form of a low molecular weight compound and a form of being incorporated into a part of a polymer in combination.

[0325] 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.

[0326] When the photoacid generator is in a form in which it is incorporated into a part of a polymer, it may be incorporated into a part of the resin (A) or into a resin different from the resin (A).

[0327] In the present invention, the photoacid generator is preferably in the form of a low molecular weight compound.

[0328] The photoacid generator is not particularly limited as long as it is a known compound, but is preferably a compound that generates at least one of an organic acid, such as a sulfonic acid, a bis(alkylsulfonyl)imide, or a tris(alkylsulfonyl)methide, upon irradiation with actinic rays or radiation, preferably an electron beam or extreme ultraviolet light.

[0329] More preferred examples include compounds represented by the following general formulae (ZI), (ZII) and (ZIII).

[0330] [ka]

[0331] In the above general formula (ZI), R 201 , R 202 and R 203 each independently represents an organic group. R 201 , R 202 and R 203 The organic group as the alkyl group generally has 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms.

[0332] Also, R 201 ~R 203 Two of these 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 203Examples of the group formed by combining two of the above include an alkylene group (for example, a butylene group, a pentylene group).

[0333] Z - represents a non-nucleophilic anion (an anion with a significantly reduced ability to undergo nucleophilic reactions).

[0334] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, tris(alkylsulfonyl)methide anions, etc.

[0335] The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, and preferred examples include linear or branched alkyl groups having 1 to 30 carbon atoms and cycloalkyl groups having 3 to 30 carbon atoms.

[0336] The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, or a naphthyl group.

[0337] The alkyl group, cycloalkyl group and aryl group mentioned 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 alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), and a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms).

[0338] The aryl group and ring structure of each group may further include an alkyl group (preferably having 1 to 15 carbon atoms) as a substituent.

[0339] The aralkyl group in the aralkylcarboxylic acid anion is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, or a naphthylbutyl group.

[0340] An example of the sulfonylimide anion is a saccharin anion.

[0341] The alkyl group in the bis(alkylsulfonyl)imide anion and tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the substituent on these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.

[0342] Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure, which increases the acid strength.

[0343] Other non-nucleophilic anions include, for example, phosphorus fluorides (e.g., PF6 - ), boron fluorides (e.g., BF4 - ), antimony fluorides (e.g., SbF6 - ) etc.

[0344] Preferred non-nucleophilic anions include aliphatic sulfonate anions in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, aromatic sulfonate anions substituted with a fluorine atom or a group having a fluorine atom, bis(alkylsulfonyl)imide anions in which an alkyl group is substituted with a fluorine atom, and tris(alkylsulfonyl)methide anions in which an alkyl group is substituted with a fluorine atom. More preferred non-nucleophilic anions include perfluoroaliphatic sulfonate anions (still more preferably having 4 to 8 carbon atoms), benzenesulfonate anions having a fluorine atom, and even more preferred nonafluorobutanesulfonate anions, perfluorooctanesulfonate anions, pentafluorobenzenesulfonate anions, and 3,5-bis(trifluoromethyl)benzenesulfonate anions.

[0345] From the viewpoint of acid strength, it is preferable that the pKa of the generated acid is −1 or less in order to improve sensitivity.

[0346] In addition, as a preferred embodiment of the non-nucleophilic anion, an anion represented by the following general formula (AN1) can also be mentioned.

[0347] [ka]

[0348] During the ceremony, Each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. R 1 , R 2 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group, and when there are multiple R 1 , R 2 may be the same or different. L represents a divalent linking group, and when a plurality of L's are present, they may be the same or different. A represents a cyclic organic group. x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

[0349] General formula (AN1) will be explained in more detail. The alkyl group in the alkyl group substituted with a fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. In addition, the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.

[0350] 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, and of these, a fluorine atom and CF3 are preferred. It is particularly preferred that both Xf's are fluorine atoms.

[0351] R 1 , R2 The alkyl group in R may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferably, it is a perfluoroalkyl group having 1 to 4 carbon atoms. 1 , R 2 Specific examples of the alkyl group having the substituent include CF3, C2F5, C3F7, C4F9, and C5F 11 , C6F 13 , C7F 15 , C8F 17 , CH2CF3, CH2CH2CF3, CH2C2F5, CH2CH2C2F5, CH2C3F7, CH2CH2C3F7, CH2C4F9, CH2CH2C4F9, among which CF3 is preferred.

[0352] R 1 , R 2 is preferably a fluorine atom or CF3. x is preferably 1 to 10, and more preferably 1 to 5. y is preferably 0 to 4, and 0 is more preferable. z is preferably 0 to 5, and more preferably 0 to 3.

[0353] The divalent linking group for 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, and a linking group in which a plurality of these groups are linked together, and a linking group having a total of 12 or less carbon atoms is preferred. Among these, —COO—, —OCO—, —CO—, and —O— are preferred, and —COO— and —OCO— are more preferred.

[0354] In the above general formula (ANI), the combination of partial structures other than A is SO 3- -CF2-CH2-OCO-, SO 3- -CF2-CHF-CH2-OCO-, SO 3- -CF2-COO-, SO 3- -CF2-CF2-CH2-, SO 3- -CF2-CH(CF3)-OCO- is preferred.

[0355] The cyclic organic group for 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 those having aromaticity but also those having no aromaticity).

[0356] The alicyclic group may be monocyclic or polycyclic, and is preferably a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, are preferred from the viewpoint of suppressing in-film diffusibility in a post-exposure baking step and improving MEEF (mask error enhancement factor).

[0357] Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.

[0358] Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, those derived from a furan ring, a thiophene ring, and a pyridine ring are preferred.

[0359] Furthermore, examples of the cyclic organic group include lactone structures, and specific examples include lactone structures represented by the following general formulae (LC1-1) to (LC1-17).

[0360] [ka]

[0361] The cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be linear, branched, or cyclic and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic, polycyclic, or spirocyclic and preferably has 3 to 20 carbon atoms), an aryl group (which preferably has 6 to 14 carbon atoms), a hydroxy group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, a sulfonate ester group, etc. The carbon constituting the cyclic organic group (the carbon contributing to ring formation) may be a carbonyl carbon.

[0362] The above substituents correspond to Rb2 in (LC1-1) to (LC1-17). In (LC1-1) to (LC1-17), n2 represents an integer of 0 to 4. When n2 is 2 or greater, multiple Rb2 may be the same or different, and multiple Rb2 may be bonded to form a ring.

[0363] In general formula (ZI), R 201 , R 202 and R 203 Examples of the organic group include an aryl group, an alkyl group, and a cycloalkyl group.

[0364] R 201 , R 202 and R 203 Preferably, at least one of the R groups is an aryl group, and more preferably, all three groups 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 group and cycloalkyl group preferably include a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. These groups may further have a substituent. Examples of the substituent 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), and an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), but are not limited thereto.

[0365] Next, general formulae (ZII) and (ZIII) will be explained. In general formulas (ZII) and (ZIII), R 204 ~R 207 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.

[0366] R 204 ~R 207 The aryl group in R 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 having a heterocyclic structure containing 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.

[0367] R 204 ~R 207The alkyl group and cycloalkyl group in the formula (I) can preferably be a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, or a norbornyl group).

[0368] R 204 ~R 207 The aryl group, alkyl group, and cycloalkyl group in R may have a substituent. 204 ~R 207 Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group may have include an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 15 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.

[0369] In addition, in general formula (ZII), Z - represents a non-nucleophilic anion. Specifically, in general formula (ZI), Z - The preferred embodiment is also the same as that described above.

[0370] Specific examples of general formulas (ZI) to (ZIII) are shown below, but the invention is not limited to these.

[0371] [ka]

[0372] In the present invention, the photoacid generator is a compound that can be used to form a film having a volume of 130 Å by irradiation with an electron beam or extreme ultraviolet light, from the viewpoint of suppressing the diffusion of the acid generated by exposure to the non-exposed area and improving the resolution. 3 The compound may be a compound that generates an acid (more preferably a sulfonic acid) having a volume of 190 Å or more. 3 It is more preferable that the compound generates an acid (more preferably a sulfonic acid) having a volume of 270 Å or more. 3It is more preferable that the compound is a compound that generates an acid (more preferably a sulfonic acid) having a volume of 400 Å or more. 3 However, from the viewpoint of sensitivity and solubility in a coating solvent, the above volume is preferably 2000 Å or more. 3 Preferably, it is 1500 Å or less. 3 The above volume values ​​were determined using "WinMOPAC" manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid in each example is input, and then the most stable conformation of each acid is determined by molecular force field calculation using the MM3 method with this structure as the initial structure. Thereafter, molecular orbital calculations using the PM3 method are performed on these most stable conformations, thereby allowing the "accessible volume" of each acid to be calculated.

[0373] In the present invention, photoacid generators that generate the acids exemplified below upon irradiation with actinic rays or radiation are preferred. Note that some of the examples include calculated values ​​for volume (unit: Å). 3 ) The calculated value here is the volume of the acid with a proton bonded to the anion portion.

[0374] [ka]

[0375] [ka]

[0376] [ka]

[0377] As for the photoacid generator, paragraphs

[0368] to

[0377] of JP 2014-41328 A and paragraphs

[0240] to

[0262] of JP 2013-228681 A (corresponding paragraph

[0339] of U.S. Patent Application Publication No. 2015 / 004533) can be cited, the contents of which are incorporated herein by reference. Specific preferred examples include, but are not limited to, the following compounds:

[0378] [ka]

[0379] [ka]

[0380] [ka]

[0381] [ka]

[0382] The photoacid generators can be used singly or in combination of two or more.

[0383] The content of the photoacid generator in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 0.1 to 50 mass %, more preferably 5 to 50 mass %, and even more preferably 8 to 40 mass %, based on the total solid content of the composition. In particular, to achieve both high sensitivity and high resolution upon exposure to electron beams or extreme ultraviolet rays, the content of the photoacid generator is preferably high, more preferably 10 to 40 mass %, and most preferably 10 to 35 mass %.

[0384] (C) Solvent A solvent can be used when preparing the actinic ray- or radiation-sensitive resin composition by dissolving the above-mentioned components. 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 which may contain a ring, alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates.

[0385] 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.

[0386] 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.

[0387] Preferred examples of alkyl lactate include methyl lactate, ethyl lactate, propyl lactate, and butyl lactate.

[0388] Preferred examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.

[0389] Preferred examples of cyclic lactones having 4 to 10 carbon atoms include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-octanoic lactone, and α-hydroxy-γ-butyrolactone.

[0390] Examples of monoketone compounds 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, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2- Preferred examples include 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, and 3-methylcycloheptanone.

[0391] Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.

[0392] Preferred examples of the alkoxy alkyl acetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-2-propyl acetate.

[0393] Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

[0394] Preferred examples of solvents that can be used include solvents with a boiling point of 130° C. or higher at room temperature and normal pressure, such as 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. In the present invention, the above solvents may be used alone or in combination of two or more kinds.

[0395] In the present invention, a mixed solvent obtained by mixing a solvent containing a hydroxyl group in its structure with a solvent not containing a hydroxyl group may be used as the organic solvent.

[0396] Examples of the solvent containing a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethyl lactate, with propylene glycol monomethyl ether and ethyl lactate being particularly preferred.

[0397] Examples of the solvent not containing a hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N,N-dimethylacetamide, and dimethyl sulfoxide. Of these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, and 2-heptanone are most preferred.

[0398] The mixing ratio (by mass) of the solvent containing a hydroxyl group to the solvent not containing a hydroxyl group is preferably 1 / 99 to 99 / 1, more preferably 10 / 90 to 90 / 10, and even more preferably 20 / 80 to 60 / 40. A mixed solvent containing 50 mass % or more of a solvent not containing a hydroxyl group is particularly preferred in terms of coating uniformity.

[0399] The solvent is preferably a mixed solvent of two or more types containing propylene glycol monomethyl ether acetate. As the solvent, for example, the solvents described in paragraphs 0013 to 0029 of JP-A No. 2014-219664 can also be used.

[0400] (D) Basic compounds The actinic ray-sensitive or radiation-sensitive resin composition preferably contains a basic compound (D) in order to reduce changes in performance over time from exposure to heating.

[0401] Preferred examples of the basic compound (D) include compounds having structures represented by the following formulas (A) to (E).

[0402] [ka]

[0403] In the general formulae (A) and (E), R 200 , R201 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), where R 201 and R 202 may be bonded to each other to form a ring.

[0404] With regard to the alkyl group, the alkyl group having a substituent is preferably 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. R 203 , R 204 , R 205 and R 206 may be the same or different and represent an alkyl group having 1 to 20 carbon atoms. The alkyl groups in these general formulae (A) and (E) are more preferably unsubstituted.

[0405] Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, etc., and more preferred compounds include compounds having an imidazole structure, a diazabicyclo 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.

[0406] Compounds having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, etc. Compounds having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, 1,8-diazabicyclo[5,4,0]undec-7-ene, etc. Compounds having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxides having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, etc. Compounds having an onium carboxylate structure include compounds having an onium hydroxide structure in which the anion moiety is carboxylate, such as acetate, adamantane-1-carboxylate, and perfluoroalkyl carboxylate. Compounds having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Aniline compounds include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Alkylamine derivatives having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, and tris(methoxyethoxyethyl)amine. Aniline derivatives having a hydroxyl group and / or an ether bond include N,N-bis(hydroxyethyl)aniline.

[0407] Further preferred basic compounds include amine compounds having a phenoxy group and ammonium salt compounds having a phenoxy group.

[0408] The amine compound may be a primary, secondary, or tertiary amine compound, and is preferably an amine compound having at least one alkyl group bonded to the nitrogen atom. The amine compound is more preferably a tertiary amine compound. As long as the amine compound has at least one alkyl group (preferably having 1 to 20 carbon atoms) bonded to the 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 the nitrogen atom in addition to the alkyl group.

[0409] Furthermore, the amine compound preferably has an oxygen atom in the alkyl chain to form an oxyalkylene group. The number of oxyalkylene groups in the molecule is one or more, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (-CH2CHO-) or an oxypropylene group (-CH(CH3)CHO- or -CH2CH2CHO-) is preferred, and an oxyethylene group is more preferred.

[0410] The ammonium salt compound may be a primary, secondary, tertiary, or quaternary ammonium salt compound, and is preferably an ammonium salt compound having at least one alkyl group 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 the 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 the nitrogen atom in addition to the alkyl group.

[0411] The ammonium salt compound preferably has an oxygen atom in the alkyl chain to form an oxyalkylene group. The number of oxyalkylene groups in the molecule is one or more, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (-CH2CHO-) or an oxypropylene group (-CH(CH3)CHO- or -CH2CH2CHO-) is preferred, and an oxyethylene group is more preferred.

[0412] Examples of anions of ammonium salt compounds include halogen atoms, sulfonates, borates, and phosphates, with halogen atoms and sulfonates being preferred. Chloride, bromide, and iodide are particularly preferred halogen atoms, and organic sulfonates having 1 to 20 carbon atoms are particularly preferred sulfonates. Examples of organic sulfonates include alkyl sulfonates and aryl sulfonates having 1 to 20 carbon atoms. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, an alkoxy group, an acyl group, and an aryl group. Specific examples of alkyl sulfonates include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate. Examples of the aryl group of the aryl sulfonate include a benzene ring, a naphthalene ring, and an anthracene ring. The benzene ring, naphthalene ring, and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the linear or branched alkyl group and the cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl, and cyclohexyl. Other examples of the substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.

[0413] An amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group are amine compounds or ammonium salt compounds having a phenoxy group at the end opposite to the nitrogen atom of the alkyl group of the amine compound or ammonium salt compound. The phenoxy group may have a substituent. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. The substitution position of the substituent may be any of the 2nd to 6th positions. The number of substituents may be any within the range of 1 to 5.

[0414] It is preferable that at least one oxyalkylene group is present between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups in the molecule is one or more, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (-CH2CHO-) or an oxypropylene group (-CH(CH3)CHO- or -CH2CH2CHO-) is preferred, and an oxyethylene group is more preferred.

[0415] The amine compound having a phenoxy group can be obtained by heating a primary or secondary amine having a phenoxy group to react with a haloalkyl ether, adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, or tetraalkylammonium, and then extracting with an organic solvent such as ethyl acetate or chloroform. Alternatively, the amine compound can be obtained by heating a primary or secondary amine to react with a haloalkyl ether having a phenoxy group at its terminal, adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, or tetraalkylammonium, and then extracting with an organic solvent such as ethyl acetate or chloroform. (Compound (PA) that has a proton-accepting functional group and decomposes upon irradiation with actinic rays or radiation to generate a compound in which the proton-accepting property is reduced or eliminated, or which has changed from a proton-accepting property to an acidic compound) The composition according to the present invention may further contain, as a basic compound, a compound having a proton-accepting functional group and decomposing upon irradiation with actinic rays or radiation to generate a compound whose proton-accepting property is reduced or eliminated, or whose proton-accepting property is changed from a proton-accepting property to an acidic property (hereinafter, also referred to as compound (PA)).

[0416] The proton acceptor functional group is a functional group having a group or electrons capable of electrostatically interacting with a proton, and refers to, 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 nitrogen atom with an unshared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula:

[0417] [ka]

[0418] Preferred partial structures of the proton acceptor functional group include, for example, crown ether, azacrown ether, primary to tertiary amine, pyridine, imidazole, and pyrazine structures.

[0419] When irradiated with actinic rays or radiation, the compound (PA) decomposes to generate a compound in which its proton acceptor property is reduced or eliminated, or which has changed from proton acceptor property to acidic. Here, the reduction or elimination of proton acceptor property, or the change from proton acceptor property to acidic, refers to a change in proton acceptor property resulting from the addition of a proton to a proton acceptor functional group. Specifically, when a proton adduct is formed from the compound (PA) having a proton acceptor functional group and a proton, the equilibrium constant in the chemical equilibrium decreases.

[0420] Specific examples of the compound (PA) include the following compounds: Further, specific examples of the compound (PA) can be cited, for example, those described in paragraphs 0421 to 0428 of JP 2014-41328 A and paragraphs 0108 to 0116 of JP 2014-134686 A, the contents of which are incorporated herein by reference.

[0421] [ka]

[0422] [ka]

[0423] [ka]

[0424] These basic compounds may be used alone or in combination of two or more.

[0425] The amount of the basic compound used is usually from 0.001 to 10 mass %, and preferably from 0.01 to 5 mass %, based on the solid content of the actinic ray-sensitive or radiation-sensitive composition.

[0426] The ratio of the photoacid generator to the basic compound used in the composition is preferably photoacid generator / basic compound (molar ratio) = 2.5 to 300. That is, from the viewpoints of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing a decrease in resolution due to thickening of the resist pattern over time after exposure until 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 even more preferably 7.0 to 150.

[0427] As the basic compound, for example, compounds described in paragraphs 0140 to 0144 of JP-A No. 2013-11833 (amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc.) can be used.

[0428] (A') Hydrophobic resin The actinic ray-sensitive or radiation-sensitive resin composition may contain a hydrophobic resin (A') in addition to the resin (A).

[0429] The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily have to have a hydrophilic group in its molecule, and it does not necessarily have to contribute to uniform mixing of polar and non-polar substances. The effects of adding a hydrophobic resin include controlling the static and dynamic contact angle of the resist film surface with water and suppressing outgassing.

[0430] From the viewpoint of uneven distribution in the film surface layer, the hydrophobic resin preferably contains one or more of "fluorine atoms," "silicon atoms," and "CH3 partial structures contained in the side chain portion of the resin," and more preferably contains two or more of them. Furthermore, the hydrophobic resin preferably contains a hydrocarbon group having 5 or more carbon atoms. These groups may be contained in the main chain of the resin or may be substituted on the side chain.

[0431] When the hydrophobic resin contains a fluorine atom and / or a silicon atom, the fluorine atom and / or the silicon atom in the hydrophobic resin may be contained in the main chain or in the side chain of the resin. When the hydrophobic resin contains a fluorine atom, it is preferable that the hydrophobic resin has, as a partial structure having a fluorine atom, an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom.

[0432] The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably having 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom has been substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.

[0433] The fluorine atom-containing cycloalkyl group 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.

[0434] Examples of aryl groups having a fluorine atom include aryl groups such as phenyl and naphthyl groups in which at least one hydrogen atom has been substituted with a fluorine atom, and the aryl group may further have a substituent other than a fluorine atom.

[0435] Examples of repeating units having a fluorine atom or a silicon atom include those exemplified in paragraph 0519 of US2012 / 0251948A1.

[0436] As described above, the hydrophobic resin also preferably contains a CH3 partial structure in the side chain portion. Here, the CH3 partial structure possessed by the side chain portion in the hydrophobic resin includes the CH3 partial structure possessed by an ethyl group, a propyl group, and the like.

[0437] On the other hand, methyl groups directly bonded to the main chain of the hydrophobic resin (for example, α-methyl groups of repeating units having a methacrylic acid structure) are not included in the CH3 partial structure of the present invention because they have little contribution to the uneven distribution of the hydrophobic resin on the surface due to the influence of the main chain.

[0438] For details regarding hydrophobic resins, please refer to the descriptions in

[0348] to

[0415] of JP 2014-010245 A, the contents of which are incorporated herein by reference. In addition, hydrophobic resins described in JP-A Nos. 2011-248019, 2010-175859, and 2012-032544 can also be preferably used.

[0439] (E) Surfactant The actinic ray-sensitive or radiation-sensitive resin composition may further contain a surfactant (E). By containing the surfactant, it becomes possible to form a pattern with good sensitivity and resolution, good adhesion, and fewer development defects when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less, is used.

[0440] As the surfactant, it is particularly preferable to use a fluorine-based and / or silicon-based surfactant.

[0441] Examples of fluorine-based and / or silicone-based surfactants include those described in paragraph

[0276] of U.S. Patent Application Publication No. 2008 / 0248425. Other examples include Eftop EF301 or EF303 (manufactured by Shin-Akita Chemical Industry Co., Ltd.); Fluorad FC430, 431, or 4430 (manufactured by Sumitomo 3M Limited); Megafac F171, F173, F176, F189, F113, F110, F177, F120, or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105, or 106 (manufactured by Asahi Glass Co., Ltd.); Troisol S-366 (manufactured by Troy Chemical Co., Ltd.); and GF-300 or GF-150 (manufactured by Toa Gosei Chemical Co., Ltd.). (manufactured by Seimi Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); F-TOP EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, or EF601 (manufactured by JEMCO Corporation); PF636, PF656, PF6320, or PF6520 (manufactured by OMNOVA); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, or 222D (manufactured by Neos Corporation). Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

[0442] In addition to the known surfactants listed above, the surfactant may be synthesized using a fluoroaliphatic compound produced by the telomerization method (also called the telomer method) or the oligomerization method (also called the oligomer method). Specifically, a polymer having a fluoroaliphatic group derived from the fluoroaliphatic compound may be used as the surfactant. The fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991.

[0443] Furthermore, surfactants other than fluorine-based and / or silicone-based surfactants described in paragraph

[0280] of US Patent Application Publication No. 2008 / 0248425 may also be used. These surfactants may be used alone or in combination of two or more.

[0444] 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 even more preferably 0.0005 to 1 mass %, based on the total solid content of the composition.

[0445] (F) Other additives The actinic ray-sensitive 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 (for example, a phenol compound having a molecular weight of 1,000 or less, or an alicyclic or aliphatic compound containing a carboxy group).

[0446] The actinic ray-sensitive or radiation-sensitive resin composition may further contain a dissolution-inhibiting compound.

[0447] Here, the "dissolution inhibiting compound" is a compound with a molecular weight of 3000 or less that is decomposed by the action of an acid and has a reduced solubility in an organic developer.

[0448] [Upper layer (top coat)] In the pattern forming method of the present invention, an upper layer film (topcoat film) may be formed on the resist film.

[0449] It is preferable that the upper layer film does not mix with the resist film and can be applied uniformly onto the resist film.

[0450] The upper layer film is not particularly limited, and a conventionally known upper layer film can be formed by a conventionally known method, for example, based on the description in paragraphs 0072 to 0082 of JP 2014-059543 A. As a material for forming the upper layer film, in addition to the polymers described in paragraph 0072 of JP 2014-059543 A, hydrophobic resins and the like can also be used. As the hydrophobic resin, for example, the above-described hydrophobic resin (A') can be used.

[0451] When a developer containing an organic solvent is used in the development step, it is preferable to form an upper layer film containing a basic compound on the resist film, such as that described in JP-A-2013-61648. Specific examples of the basic compound that the upper layer film may contain include basic compound (E).

[0452] The upper layer film preferably contains a compound containing 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.

[0453] Furthermore, the upper layer film may contain a photoacid generator. As the photoacid generator, the same photoacid generators as those that can be contained in the actinic ray-sensitive or radiation-sensitive composition (for example, the above-mentioned photoacid generator (B)) can be used.

[0454] Resins that are preferably used for the upper layer film (top coat film) will be described below.

[0455] (resin) The composition for forming an upper layer film preferably contains a resin. The resin that can be contained in the composition for forming an upper layer film is not particularly limited, but the same hydrophobic resin as that which can be contained in the actinic ray-sensitive or radiation-sensitive composition (for example, the above-mentioned hydrophobic resin (A')) can be used.

[0456] With regard to the hydrophobic resin, reference can be made to paragraphs

[0017] to

[0023] of JP 2013-61647 A (corresponding paragraphs

[0017] to

[0023] of U.S. Patent Publication No. 2013 / 244438 A) and paragraphs

[0016] to

[0165] of JP 2014-56194 A, the contents of which are incorporated herein by reference.

[0457] In the present invention, the composition for forming the upper layer film preferably contains a resin containing a repeating unit having an aromatic ring. By containing a repeating unit having an aromatic ring, the efficiency of secondary electron generation and the efficiency of acid generation from a compound that generates acid by actinic rays or radiation are increased, particularly during exposure to electron beams or EUV, and the effects of high sensitivity and high resolution can be expected during pattern formation. The weight average molecular weight of the resin is preferably 3,000 to 100,000, more preferably 3,000 to 30,000, and most preferably 5,000 to 20,000. The amount of the resin in the composition for forming an upper layer film is preferably 50 to 99.9 mass %, more preferably 60 to 99.0 mass %, even more preferably 70 to 99.7 mass %, and even more preferably 80 to 99.5 mass %, based on the total solid content.

[0458] When the composition for forming an upper layer film (top coat composition) contains a plurality of resins, it is preferable that it contains at least one resin (XA) having a fluorine atom and / or a silicon atom.

[0459] The preferred range of the content of fluorine atoms and silicon atoms contained in resin (XA) is such that the repeating units containing fluorine atoms and / or silicon atoms in resin (XA) are preferably 10 to 100 mass %, more preferably 10 to 99 mol %, and even more preferably 20 to 80 mol %.

[0460] It is more preferable that the composition for forming an upper layer film contains at least one resin (XA) having fluorine atoms and / or silicon atoms, and a resin (XB) having a lower content of fluorine atoms and / or silicon atoms than that of the resin (XA). This allows the resin (XA) to be unevenly distributed on the surface of the upper layer film when the upper layer film is formed, thereby improving performance such as development characteristics and immersion liquid followability.

[0461] The content of resin (XA) is preferably 0.01 to 30 mass%, more preferably 0.1 to 10 mass%, even more preferably 0.1 to 8 mass%, and particularly preferably 0.1 to 5 mass%, based on the total solid content of the composition for forming an upper layer film. The content of resin (XB) is preferably 50.0 to 99.9 mass%, more preferably 60 to 99.9 mass%, even more preferably 70 to 99.9 mass%, and particularly preferably 80 to 99.9 mass%, based on the total solid content of the composition for forming an upper layer film.

[0462] Resin (XB) is preferably in a form that is substantially free of 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%, still more preferably 0 to 5 mol%, particularly preferably 0 to 3 mol%, and ideally 0 mol%, i.e., no fluorine atoms or silicon atoms are contained, based on the total repeating units in resin (XB).

[0463] <Method for preparing composition for forming upper layer film (top coat composition)> The composition for forming an upper layer film is preferably prepared by dissolving each component in a solvent and filtering the resulting solution through a filter. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon, with a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. Multiple types of filters may be connected in series or parallel. The composition may be filtered multiple times, and the process of filtering multiple times may be a circulating filtration process. Furthermore, the composition may be subjected to a degassing treatment before or after filtering. The composition for forming an upper layer film is preferably free of impurities such as metals. The content of metal components contained in these materials is preferably 10 ppm or less, more preferably 5 ppm or less, even more preferably 1 ppm or less, and it is particularly preferred that the composition is substantially free of metals (below the detection limit of the measuring device).

[0464] In the above-mentioned "exposure step," when the exposure is performed by immersion exposure, the upper layer film is disposed between the actinic ray-sensitive or radiation-sensitive film and the immersion liquid, and also functions as a layer that prevents the actinic ray-sensitive or radiation-sensitive film from directly contacting the immersion liquid. In this case, the upper layer film (composition for forming the upper layer film) preferably has properties such as suitability for application to the actinic ray-sensitive or radiation-sensitive film, transparency to radiation, particularly at 193 nm, and poor solubility in the immersion liquid (preferably water). Furthermore, it is preferable that the upper layer film does not mix with the actinic ray-sensitive or radiation-sensitive film and can be uniformly applied to the surface of the actinic ray-sensitive or radiation-sensitive film.

[0465] In order to uniformly apply the composition for forming an upper layer film to 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. It is more preferable to use a solvent that does not dissolve the actinic ray-sensitive or radiation-sensitive film, the solvent having components different from those of a developer containing an organic solvent (organic developer).

[0466] The method for applying the composition for forming the upper layer film is not particularly limited, and conventionally known methods such as spin coating, spraying, roller coating, and dipping can be used.

[0467] The thickness of the upper layer film is not particularly limited, but from the viewpoint of transparency to the exposure light source, it is usually formed to a thickness of 5 nm to 300 nm, preferably 10 nm to 300 nm, more preferably 20 nm to 200 nm, and even more preferably 30 nm to 100 nm.

[0468] After the upper layer film is formed, the substrate is heated (PB) as necessary. 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. The upper layer film is preferably insoluble in the immersion liquid, more preferably insoluble in water. From the viewpoint of immersion liquid followability, the receding contact angle of the upper layer film (23°C) of the immersion liquid to the upper layer film is preferably 50 to 100 degrees, more preferably 80 to 100 degrees.

[0469] In immersion exposure, the immersion liquid must move over the wafer in response to the movement of the exposure head, which scans the wafer at high speed to form an exposure pattern. Therefore, the contact angle of the immersion liquid with the actinic ray-sensitive or radiation-sensitive film in a dynamic state becomes important, and in order to obtain better resist performance, it is preferable that the immersion liquid have a receding contact angle within the above range.

[0470] When peeling off the upper layer film, an organic developer may be used, or a separate stripping solution may be used. A solvent with low permeability into the actinic ray-sensitive or radiation-sensitive film is preferred as the stripping solution. In order to allow peeling off of the upper layer film and development of the actinic ray-sensitive or radiation-sensitive film to occur simultaneously, it is preferred that the upper layer film be peeled off with an organic developer. The organic developer used for peeling off is not particularly limited as long as it can dissolve and remove the low-exposure areas of the actinic ray-sensitive or radiation-sensitive film.

[0471] From the viewpoint of peeling off with an organic developer, the dissolution rate of the upper layer film in an organic developer is preferably 1 to 300 nm / sec, more preferably 10 to 100 nm / sec.

[0472] Here, the dissolution rate of the upper layer film in an organic developer refers to the rate at which the film thickness decreases when the upper layer film is exposed to a developer after it has been formed, and in the present invention, this refers to the rate at which the film is immersed in butyl acetate at 23°C.

[0473] By setting the dissolution rate of the upper layer film in an organic developer to 1 / sec or more, preferably 10 nm / sec or more, the occurrence of development defects after development of the actinic ray-sensitive or radiation-sensitive film is reduced. Also, by setting the dissolution rate to 300 nm / sec or less, preferably 100 nm / sec, the line edge roughness of the pattern after development of the actinic ray-sensitive or radiation-sensitive film is improved, probably due to the effect of reducing exposure unevenness during immersion exposure.

[0474] The upper layer film may be removed using other known developers, such as an aqueous alkaline solution, etc. Specific examples of aqueous alkaline solutions that can be used include an aqueous solution of tetramethylammonium hydroxide.

[0475] The present invention also relates to a method for producing an electronic device, which includes the above-described pattern forming method of the present invention.

[0476] The electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitable for incorporation into electrical and electronic equipment (such as home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment). [Example]

[0477] The present invention will be described in detail below with reference to examples, but the content of the present invention is not limited thereto. Unless otherwise specified, "%", "ppb", and "ppt" are based on mass.

[0478] <<Preparation of processing solutions for semiconductor manufacturing>> Examples of synthesis of various treatment liquids are described below, but the present invention is not limited to these examples and the liquids can be synthesized using known methods.

[0479] [Examples 1 to 46, Comparative Examples 1 and 2] <Refining raw materials, etc.> The raw materials and catalysts used in the examples shown below are of high purity grade with a purity of 99% by mass or more, and are further purified in advance by distillation, ion exchange, filtration, etc. The catalyst used in the esterification reaction shown below is sulfuric acid. The sulfuric acid used as this catalyst has a purity of 98% by mass or more, but it can also be used by supplying dilute sulfuric acid and dehydrating it to a predetermined concentration range.

[0480] The ultrapure water used in the examples was purified by the method described in JP 2007-254168 A, and the content of each of the elements Na, Ca, and Fe was confirmed to be less than 10 ppt by mass relative to the total mass of each treatment solution by measurement using the SP-ICP-MS method described below, and then used to prepare the treatment solution.

[0481] Preparation, filling, storage, and analytical measurements of the processing solution were all carried out in a clean room meeting ISO Class 2 or lower. The containers used in the examples were washed in advance with the processing solution of the present invention before use.

[0482] <Synthesis Example 1> Synthesis of butyl acetate-containing treatment solution (treatment solution 1A) (Process 1) Acetic acid and n-butanol were preliminarily reacted in a continuous tank reactor in the presence of sulfuric acid as a catalyst. The resulting reaction solution 1a was then reacted in a continuous reactive distillation column while removing water, by-produced as an azeotropic mixture of butyl acetate, n-butanol, and water, from the top of the distillation column to give a crude liquid containing butyl acetate (hereinafter referred to as "crude butyl acetate liquid") 1b.

[0483] (Process 2) The sulfuric acid content of the crude butyl acetate liquid 1b obtained in step 1 was neutralized with alkali, and then the crude butyl acetate liquid 1c was obtained by washing with water and removing the moisture.

[0484] (Step 3) The butyl acetate crude liquid 1c obtained in step 2 was neutralized and washed with water, and most of the water and sulfuric acid were separated using a decanter. Next, the butyl acetate crude liquid 1d containing butyl acetate, n-butanol, water, sulfuric acid, and trace amounts of by-products was fed to a distillation column to remove impurities such as n-butanol and low-boiling points such as water. The distillation was then repeated multiple times to obtain the target product, a butyl acetate-containing treated liquid (treated liquid 1A).

[0485] The compound (B) contained in the resulting butyl acetate-containing treatment liquid (treatment liquid 1A) was the following compound. The content of each of these compounds in the treatment liquid satisfied requirement (b) (see Table 2).

[0486] [ka]

[0487] Other butyl acetate-containing treatment solutions (treatment solutions 1B to 1Q) were synthesized using the same method as in Synthesis Example 1. The compound (B) contained in each of the resulting treatment solutions was the same as that contained in treatment solution 1A, and the content of each compound (B) in the treatment solution satisfied requirement (b) (see Table 2).

[0488] <Synthesis Example 2> Synthesis of 1-hexanol-containing treatment solution (treatment solution 2A) (raw materials, etc.) 1-Hexanol is synthesized via the following two-step reaction scheme:

[0489] Al(C2H5)3+6C2H4 → Al(C6H 13 )3 Al(CH 13 )3+3 / 2O2+3H2O→3HOC6H 13 +Al(OH)3 (Step 1) By a known method, Al(CH) polymerized by the first step reaction described above is obtained. 15 )3 was then obtained. 151-Hexanol was synthesized using 3 as a catalyst in the presence of oxygen and water according to a known method. Heat treatment was carried out at 40°C for 10 hours to obtain a crude liquid containing 1-hexanol (hereinafter referred to as "1-hexanol crude liquid") 2a. Aluminum was removed as aluminum hydroxide.

[0490] (Process 2) The 1-hexanol crude liquid 2a obtained in step 1 contained precipitates of Al(OH)3, so Al(OH)3 was removed by filtration to obtain a 1-hexanol crude liquid 2b.

[0491] (Step 3) The 1-hexanol crude liquid 2b obtained in step 2 was supplied to a distillation column for the purpose of removing by-product substitution isomers, higher alcohols, etc. Thereafter, the distillation was repeated multiple times to obtain a 1-hexanol-containing treated liquid (treated liquid 2A) as the target product.

[0492] The compound (B) contained in the resulting 1-hexanol-containing treatment liquid (treatment liquid 2A) was the following compound. The content of each of these compounds in the treatment liquid satisfied requirement (b) (see Table 2).

[0493] [ka]

[0494] <Synthesis Example 3> Synthesis of 4-methyl-2-pentanol-containing treatment solution (treatment solution 3A) (Process 1) 4-Methyl-2-pentanol was synthesized from cis-4-methyl-2-pentene in the presence of IpcBH (Diisopinocampheylborane) as a catalyst according to a known method. Heat treatment was carried out at 80°C for 4 hours to obtain a crude liquid containing 4-methyl-2-pentanol (hereinafter referred to as "4-methyl-2-pentanol crude liquid") 3a via an intermediate in which cis-4-methyl-2-pentene and IpcBH were bonded via boron.

[0495] (Process 2) The crude 4-methyl-2-pentanol liquid 3a obtained in step 1 contains unreacted cis-4-methyl-2-pentene and substitution isomers as impurities. This 4-methyl-2-pentanol crude liquid 3a was supplied to a distillation column for purification, and the distillation was repeated multiple times to obtain a 4-methyl-2-pentanol-containing treated liquid (treated liquid 3A) as the target product.

[0496] The compound (B) contained in the resulting 4-methyl-2-pentanol-containing treatment liquid (treatment liquid 3A) was the following compound. The content of each of these compounds in the treatment liquid satisfied requirement (b) (see Table 2).

[0497] [ka]

[0498] Other 4-methyl-2-pentanol-containing treatment solutions (treatment solutions 3B to 3G) were synthesized in the same manner as in Synthesis Example 3. The compound (B) contained in each of the resulting treatment solutions was the same as that contained in treatment solution 1A, and the content of each compound (B) in the treatment solution satisfied requirement (b) (see Table 2).

[0499] <Synthesis Example 4> Synthesis of PGMEA (propylene glycol monomethyl ether acetate)-containing treatment solution (treatment solution 4A) (Process 1) PGMEA was synthesized (two-step synthesis) from propylene oxide, methanol, and acetic acid in the presence of sulfuric acid as a catalyst according to a known method, whereby a crude PGMEA-containing solution (hereinafter referred to as "PGMEA crude solution") 4a was obtained by heat treatment at 80°C for 8 hours.

[0500] (Process 2) The PGMEA crude liquid 4a obtained in step 1 contains unreacted propylene oxide, methanol, acetic acid, and substitution isomers as impurities. This PGMEA crude liquid 4a was fed to a distillation column for purification, and the distillation was repeated several times to obtain the target product, a PEGMEA-containing treated liquid (treated liquid 4A). The compound (B) contained in the resulting PGMEA-containing treatment solution (treatment solution 4A) was the following compound. The content of each of these compounds in the treatment solution satisfied requirement (b) (see Table 2).

[0501] [ka]

[0502] Other PGMEA-containing treatment solutions (treatment solutions 4B to 4E) were synthesized in the same manner as in Synthesis Example 4. The compound (B) contained in each of the resulting treatment solutions was the same as that in treatment solution 4A, and the content of each compound (B) in the treatment solution satisfied requirement (b) (see Table 2).

[0503] <Synthesis Example 5> Synthesis of IPA (isopropanol)-containing processing solution (processing solution 5A) (Process 1) Acetone was reduced using acetone and hydrogen in the presence of copper oxide-zinc oxide-aluminum oxide as a catalyst according to a known method, whereby a heat 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.

[0504] (Process 2) The crude IPA solution 5a contained unreacted acetone, substitution isomers as impurities, and the catalyst. This crude IPA solution 5a was fed to a distillation column for purification. Distillation was repeated multiple times to obtain the target product, an IPA-containing treated solution (treated solution 5A).

[0505] The compound (B) contained in the resulting IPA-containing treatment liquid (treatment liquid 5A) was the following compound. The content of each of these compounds in the treatment liquid satisfied requirement (b) (see Table 2).

[0506] [ka]

[0507] 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 contained in treatment liquid 5A, and the content of compound (B) in each of the treatment liquids satisfied requirement (b) (see Table 2).

[0513] <Synthesis Example 7> Synthesis of cyclohexanone-containing treatment solution (treatment solution 7A) (Process 1) According to the method described in JP 2007-63209 A, monochlorobenzene and hydrogen chloride were obtained from benzene and chlorine. Next, phenol and hydrogen chloride were obtained from monochlorobenzene and water. Next, a crude liquid containing cyclohexanone (hereinafter referred to as "crude cyclohexanone liquid") 7a was obtained from phenol and hydrogen.

[0514] (Process 2) In step 1, the crude cyclohexanone liquid 7a obtained from the reaction column contains unreacted benzene, monochlorobenzene, phenol, and the like. The obtained cyclohexanone crude liquid 7a was supplied to a distillation column for purification, and then distillation was repeated several times to obtain a cyclohexanone-containing treated liquid (treated liquid 7A).

[0515] The compound (B) contained in the resulting cyclohexanone-containing treatment liquid (treatment liquid 7A) was the following compound. The content of each of these compounds in the treatment liquid satisfied requirement (b) (see Table 2).

[0516] [ka]

[0517] Another cyclohexanone-containing treatment liquid (treatment liquid 7E) was synthesized using the same method as in Synthesis Example 7. Treatment liquids 7B to 7D and 7F to 7G were prepared by purifying crude liquid 7a using the method described below. The compound (B) contained in each of the treatment liquids obtained was the same as that in treatment liquid 7A, and the content of compound (B) in each treatment liquid satisfied requirement (b) (see Table 2).

[0518] <Synthesis Example 8> Synthesis of PGME (propylene glycol monomethyl ether)-containing treatment solution (treatment solution 8A) (Process 1) According to the method described in JP-A-2008-208035, methanol and propylene oxide were reacted at 90 to 110° C. to obtain a crude liquid containing PGME (hereinafter referred to as “PGME crude liquid”) 8a.

[0519] (Process 2) In step 1, the crude PGME liquid 8a obtained from the reaction column contains unreacted methanol, propylene oxide, catalytic tertiary amine, and the like. The obtained crude PGME liquid 8a was supplied to a distillation column for purification, and then distillation was repeated several times to obtain a PGME-containing treated liquid (treated liquid 8A).

[0520] The compound (B) contained in the resulting PGME-containing treatment solution (treatment solution 8A) was the following compound. The content of each of these compounds in the treatment solution satisfied requirement (b) (see Table 2).

[0521] [ka]

[0522] <Synthesis Example 9> Synthesis of MMP (methyl 3-methoxypropionate)-containing treatment solution (treatment solution 8A) (Process 1) According to the method described in JP 2007-63209 A, methanol, the basic catalyst potassium t-butoxide (KOt-Bu), and 74.0 g (0.86 mol) of methyl acrylate were weighed and gradually added dropwise from the dropping funnel over approximately 1 hour. Since the addition of a small amount of methyl acrylate generates heat, the reaction temperature was controlled at 40°C while cooling with ice water. After the dropwise addition was completed, the mixture was heated and stirred at 40°C for 1 hour, for a total reaction time of 2 hours. Thereafter, 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 to separate the solid matter of the neutralized salt of the catalyst, yielding a crude liquid containing MMP (hereinafter referred to as "crude MMP liquid") 9a.

[0523] (Process 2) In step 1, the crude MMP solution 9a obtained from the reaction column contains unreacted methanol, methyl acrylate, and the like. The obtained crude MMP solution 9a was supplied to a distillation column for purification, and then distillation was repeated several times to obtain an MMP-containing treated solution (treated solution 9A).

[0524] The compound (B) contained in the resulting MMP-containing treatment solution (treatment solution 9A) was the following compound. The content of each of these compounds in the treatment solution satisfied requirement (b) (see Table 2).

[0525] [ka]

[0526] The obtained treatment solutions 1A to 1Q, 2A, 3A to 3G, 4A to 4E, and 5A to 5E 、7 A to 7G, 8A and 9A are shown in Tables 1-1 to 1-6 below. Tables 1-1 to 1-6 are collectively referred to as Table 1 below.

[0527] [Measurement by SP-ICP-MS method] 1) Preparation of standard materials Ultrapure water was measured and poured into a clean glass container, and metal particles to be measured with a median diameter of 50 nm were added to a concentration of 10,000 particles / ml. The resulting dispersion was then treated in an ultrasonic cleaner for 30 minutes and used as a standard substance for measuring transport efficiency.

[0528] 2) SNP-ICP-MS equipment used Manufacturer: PerkinElmer Model: NexION350S 3) SNP-ICP-MS measurement conditions The SNP-ICP-MS used a PFA coaxial nebulizer, a quartz cyclone-type spray chamber, and a quartz torch injector with an inner diameter of 1 mm, and the sample solution was drawn in at approximately 0.2 mL / min. The oxygen addition rate was 0.1 L / min, the plasma power was 1600 W, and the cell was purged with ammonia gas. Analysis was performed with a time resolution of 50 μs.

[0529] The metal particle content and metal atom content were measured using the following analytical software provided by the manufacturer. Metal particle content: Syngistix Nano Application Module for nanoparticle analysis "SP-ICP-MS" Metal atom content: Syngistix for ICP-MS software The results are shown in Table 1 below.

[0530] [Measurement of the content of compound (A), compound (B), and inorganic substance (C)] The components used in each example and comparative example were measured by GC / MS (Gas Chromatograph / Mass Spectrometer), LC / MS (Liquid Chromatograph / Mass Spectrometer), NMR (Nuclear Magnetic Resonance), and IC (Ion Chromatography). Organic substances were measured by GC / MS, LC / MS, and NMR, and inorganic substances were analyzed by IC. [GC / MS] (Gas chromatograph mass spectrometer) (Measurement conditions) Equipment: Shimadzu Corporation "GCMS-2020" [LC / MS] (Liquid Chromatograph Mass Spectrometer) (Measurement conditions) Equipment: Thermo Fishers "UPLC-H-Class, Xevo G2-XS QTof" [NMR] (Nuclear Magnetic Resonance) (Measurement conditions) Equipment: JEOL AL400 type Measurement nuclei: 1 H Solvent: CDCl3 [IC] (Ion Chromatography) (Measurement conditions) Device: Shimadzu Corporation "HIC-SP".

[0531] The content of each compound is shown in Table 1 below. In addition, the columns "S," "Al," "B," "N," and "K" in the inorganic substance (C) of Table 1 represent the content of inorganic substances containing S, inorganic substances containing Al, inorganic substances containing B, inorganic substances containing N, and inorganic substances containing K, respectively.

[0532] [Measurement of the dissolution rate (ER) of resist film] An organic anti-reflective film ARC29A (Nissan Chemical Industries, Ltd.) was applied to a silicon wafer and baked at 205°C for 60 seconds to form an anti-reflective film with a thickness of 78 nm. Then, a commercially available product, FAiRS-9101A12 (ArF resist composition, Fujifilm Electronic Materials Co., Ltd.), was applied using a spin coater and baked at 100°C for 60 seconds. The resulting wafer was scanned with an ArF excimer laser scanner (NA 0.75) at 25 mJ / cm. 2 The entire wafer was exposed to light at 120°C. The wafer was then heated at 120°C for 60 seconds. The wafer was cut into 2cm x 2cm pieces and immersed in each of the treatment solutions listed in Table 1 at 23°C for 10 minutes. The film thickness before and after immersion was measured using an optical film thickness measuring device, ellipsometry, and the dissolution rate (ER) was calculated. The results are shown in Table 1.

[0533] [Defect suppression performance (measurement of the number of defects)] Using a wafer surface inspection device (SP-5; manufactured by KLA Tencor), the number of particles (hereinafter referred to as "defects") with a diameter of 32 nm or more present on the surface of a 300 mm diameter silicon substrate was counted. The silicon substrate was then placed in a spin-discharge device, and while rotating, various treatment solutions listed in Table 1 were dispensed onto the surface of the silicon substrate at a flow rate of 1.5 L / min. The substrate was then rinsed and dried. The number of defects present on the silicon substrate surface was again counted using the same device (SP-5), and the difference from the initial value was taken as the number of defects. The resulting number of defects was evaluated based on the following criteria, and the results are shown in Table 1. Based on the following criteria, a rating of D indicates that the defect suppression performance required for a treatment solution for semiconductor manufacturing was achieved.

[0534] A: The number of defects was less than 50. B: The number of defects was more than 50 but less than 100. C: The number of defects was more than 100 but less than 500. D: The number of defects was more than 500 but less than 1,000. E: The number of defects exceeds 1,000.

[0535] [Table 1-1]

[0536] [Table 1-2]

[0537] [Table 1-3]

[0538] [Table 1-4]

[0539] [Table 1-5]

[0540] [Table 1-6]

[0541] [Table 2]

[0542] <Method for Purifying Treatment Solutions 7B to 7D and 7F to 7G> The crude cyclohexanone (CyHx) liquid 7a obtained above was purified by the method shown below to obtain treated liquids 7B to 7D and 7F to 7G shown in Table 1.

[0543] As a purification method, a manufacturing apparatus having a structure similar to that shown in Figure 2 was used, and treatment liquids 7B to 7D and 7F to 7G with different purities were obtained by selecting the number of distillation steps or the filtration method (pore size, material). As for the filtration method, the filters shown in Table 3 below were used in the filtration device provided in the above manufacturing apparatus, and the purity of the treatment liquid was adjusted.

[0544] Before purifying the crude liquid 7a by the above purification method, the production apparatus was washed with a cleaning solution, which was treated liquid 7E (cyclohexanone) shown in Table 1, and the treated liquid 7E was passed through the filter 10 times, and this cycle was repeated three times.

[0545] [Table 3]

[0546] In Table 3, Nylon, PTFE (polytetrafluoroethylene), and UPE (ultra-high molecular weight polyethylene) represent filters primarily composed of nylon, PTFE, and UPE, respectively. In addition, IEX-PTFE sulfric acid and IEX-PTFE carboxylic acid, IEX represents an ion exchange group, and refer to filters in which the surface of PTFE is modified with sulfonic acid or carboxylic acid, respectively.

[0547] <Creating a resist pattern> [Examples 101 to 112, Comparative Examples 101 and 102] An organic antireflective film ARC29A (Nissan Chemical Industries, Ltd.) was applied to a silicon wafer and baked at 205°C for 60 seconds to form a 78 nm thick antireflective film. A commercially available product, FAiRS-9101A12 (ArF resist composition, Fujifilm Electronic Materials Co., Ltd.), was applied thereon using a spin coater and baked at 100°C for 60 seconds to form a 150 nm thick resist film. The resulting wafer was scanned with an ArF excimer laser scanner (NA 0.75) at 25 mJ / cm. 2 Then, the film was heated at 120° C. for 60 seconds, and then developed (negative development) for 30 seconds in each of the processing solutions shown in Table 4 to obtain an L / S pattern.

[0548] For Examples 105 to 107, after the above development, rinsing was carried out for 30 seconds using each of the processing solutions shown in Table 4 to obtain an L / S pattern.

[0549] [Examples 113 to 119] An organic antireflective film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied to a silicon wafer and baked at 205°C for 60 seconds to form an antireflective film with a thickness of 78 nm. To improve coatability, a prewetting step was then performed in which the treatment solution shown in Table 3 was applied in advance. A commercially available product, FAiRS-9101A12 (ArF resist composition manufactured by Fujifilm Electronic Materials Co., Ltd.), was then applied using a spin coater and baked at 100°C for 60 seconds to form a resist film with a thickness of 150 nm. The resulting wafer was scanned with an ArF excimer laser scanner (NA 0.75) at 25 [mJ / cm 2 Then, the resist was heated at 120°C for 60 seconds, and developed (negative development) for 30 seconds with the treatment liquid shown in Table 4. The resulting pattern was rinsed with the treatment liquid shown in Table 1 to obtain an L / S pattern.

[0550] [Lithography performance] After pattern formation, the top surface of the line pattern and the space portion were observed using a length-measuring scanning electron microscope (Hitachi S9380II). The smaller the value of the formed pattern dimension, the better the performance. In the following criteria, a rating of D indicates that the resist pattern achieved the lithographic performance required. The evaluation results are shown in Table 4.

[0551] AL / S=less than 80nm BL / S = 80nm or more and less than 120nm CL / S = 120 nm or more and less than 150 nm DL / S = 150 nm or more and less than 200 nm EL / S=200nm or more

[0552] [Table 4]

[0553] <Examples 201 to 202, Comparative Example 201> Dimethyl sulfoxide (Wako Pure Chemical Industries, Ltd.) was prepared and purified by the method described in JP 2007-254168 A. After confirming that the contents of Na, Ca, and Fe were each less than 10 ppb by mass, the solution was used to prepare the treatment solution.

[0554] Example 201 Treatment liquid X-1 was prepared by mixing 90.5 parts by mass of treatment liquid 1A of Example 1 and 9.5 parts by mass of the dimethyl sulfoxide obtained above. The treatment solution X-1 contains, in addition to the treatment solution 1A and the above-mentioned dimethyl sulfoxide, two or more compounds (B) that satisfy the requirement (b) and an inorganic substance (C), and the total content of the compounds (B) is 10 -10 % by mass, and the ratio P of the compound (B) represented by formula I to the inorganic substance (C) is 10 3 ~10 -6 When the same evaluations as in Examples 1 and 101 were carried out using this treatment solution X-1, the same defect suppression performance as in Example 1 and the same lithography performance as in Example 101 were obtained.

[0555] Example 202 Treatment liquid X-2 was prepared by mixing 95 parts by mass of treatment liquid 1A of Example 1 and 5 parts by mass of the dimethyl sulfoxide obtained above.

[0556] In addition to the treatment solution 1A and the above-mentioned dimethyl sulfoxide, the treatment solution X-2 contains two or more compounds (B) that satisfy the requirement (b) and an inorganic substance (C), and the total content of the compounds (B) is 10 -10 % by mass, and the ratio P of the compound (B) represented by formula I to the inorganic substance (C) is 10 3 ~10 -6 When the same evaluations as in Examples 1 and 101 were carried out using this treatment solution X-2, the same defect suppression performance as in Example 1 and the same lithography performance as in Example 101 were obtained.

[0557] Comparative Example 201 Treatment solution X-3 was prepared by mixing 85 parts by mass of treatment solution 1A from Example 1 with 15 parts by mass of the dimethyl sulfoxide obtained above. When this treatment solution X-3 was used to carry out the same evaluations as in Examples 1 and 101, the same results as in Example 1 were obtained, but there was residual treatment solution after rinsing, and drying took a long time.

[0558] <Examples 301 to 307> Treatment solutions 101 to 106 were prepared by mixing the first and second treatment solutions shown in Table 5 below in the ratios shown in the same table. Treatment solution 107 shown in Table 5 is treatment solution 9A prepared above. These treatment solutions 101 to 107 were evaluated for defect suppression performance using the same method as described above. Furthermore, the resist-saving properties when these treatment solutions were used as pre-wet solutions were evaluated. Furthermore, the performance when these treatment solutions were used as rinse solutions after ashing or p-CMP was evaluated. The results are shown in Table 5.

[0559] [Reduced resistivity] The resist-saving properties of each treatment liquid when used as a prewet solution were evaluated by the following method. In this specification, "having excellent resist-saving properties" means having excellent uniformity and excellent film thickness controllability, which can suppress deterioration of lithography performance and the occurrence of defects. The resist composition 1 used was as follows:

[0560] <Resist composition 1> The acid-decomposable resin, photoacid generator, quencher, hydrophobic resin, and solvent shown below were mixed together to prepare resist composition 1 with a solids concentration of 3.5 mass %. 100 parts by mass of the acid-decomposable resin shown below

[0561] [ka]

[0562] The weight average molecular weight (Mw) of the acid-decomposable resin is 7,500, and the numerical values ​​shown for each repeating unit represent mole %.

[0563] Photoacid generator shown below: 8 parts by mass

[0564] [ka]

[0565] The following four types of quencher: 5 parts by mass (total)

[0566] [ka]

[0567] The mass ratio of the quenchers is 0.1:0.3:0.3:0.2, from left to right. Of the four types of quenchers, the polymer type on the right has a weight-average molecular weight (Mw) of 5000. The numerical values ​​listed for each repeating unit indicate the molar ratio.

[0568] The following two types of hydrophobic resins: 4 parts by mass (total)

[0569] [ka]

[0570] The mass ratio of the hydrophobic resins is 0.5:0.5 from left to right. Of the two hydrophobic resins, the hydrophobic resin on the left has a weight average molecular weight (Mw) of 7000, and the hydrophobic resin on the right has a weight average molecular weight (Mw) of 8000. In each hydrophobic resin, the numerical value written for each repeating unit means the molar ratio.

[0571] Solvent 1: PGMEA (manufactured by Wako): 3 parts by weight CyHx (cyclohexanone) (manufactured by Wako Co., Ltd.): 600 parts by mass GBL (γ-butyrolactone) (manufactured by Wako Co., Ltd.): 100 parts by mass.

[0572] <Resist composition 2> Resist composition 2 was prepared under the same conditions as resist composition 1, except that solvent 2 below was used in place of solvent 1 (PGMEA:CyHx:GBL=3 parts by mass:600 parts by mass:100 parts by mass) for resist composition 1.

[0573] Solvent 2: Treatment liquid 4A (PGMEA): 3 parts by mass Treatment liquid 7D (CyHx): 600 parts by mass GBL (γ-butyrolactone) (manufactured by Wako Co., Ltd.): 100 parts by mass.

[0574] <Uniformity> First, as a control, the resist composition 1 (or resist composition 2) was directly coated onto a silicon wafer with a diameter of approximately 30 cm (12 inches) and an anti-reflective coating. A spin coater (trade name "LITHIUS", manufactured by Tokyo Electron Ltd.) was used for coating. The resulting resist film was baked at 90°C. After baking, the resist film was subjected to a 59-point map measurement using a film thickness measurement device, Lambda Ace, manufactured by Dainippon Screen Co., Ltd., to confirm the absence of coating unevenness. The term "coating unevenness" refers to a state in which the thickness of the resist film is uniform when 59 measurement points are selected in a circular pattern from the resist film to be measured and the measurement results of the resist film thickness at each measurement point are arranged two-dimensionally and observed.

[0575] Next, a silicon wafer with a diameter of approximately 30 cm (12 inches) and equipped with an anti-reflective coating was prepared separately, and each treatment solution was dropped onto it. Thereafter, the same amount of resist composition 1 (or resist composition 2) as the control was applied and baked at 90°C. The resulting resist film was observed in the same manner as above, and it was confirmed that no coating spots had occurred. Next, the amount of resist composition 1 (or resist composition 2) used was reduced to 50% by mass and 30% by mass of the control, and the same test as above was performed to check whether coating spots had occurred. The results were evaluated according to the following criteria and are shown in Table 5.

[0576] AA: When the amount of resist composition used was reduced to 30% by mass of the control, and when it was reduced to 50% by mass, no coating spots occurred. A: No coating spots occurred when the amount of resist composition used was reduced to 50% by mass of the control, but coating spots occurred when the amount was reduced to 30% by mass of the control. B: When the amount of resist composition used was reduced to 30% by mass of the control, and when it was reduced to 50% by mass, coating spots occurred.

[0577] <Film thickness control> Each treatment solution was dropped onto a silicon wafer with a diameter of approximately 30 cm (12 inches) and equipped with an anti-reflective coating. Then, the resist composition 1 (or resist composition 2) was directly coated onto the wafer so that the resulting resist film had a thickness of 8.5 nm. A spin coater (trade name "LITHIUS", manufactured by Tokyo Electron Ltd.) was used for coating. The resulting resist film was baked at 90°C. After baking, the resist film was subjected to 59-point map measurement using a film thickness measuring device, Lambda Ace, manufactured by Dainippon Screen Co., Ltd., to determine the standard deviation (hereinafter also referred to as "σ") of the resist film thickness. Next, 3σ was calculated from the standard deviation. The results were evaluated according to the following criteria and are shown in Table 5.

[0578] A: 3σ was less than 0.15 nm. B: 3σ was greater than or equal to 0.15 nm and less than 0.2 nm. C:3σ was 0.2 nm or more.

[0579] [Rinse performance after ashing removal] Resist composition 1 (or resist composition 2) was applied to a silicon wafer, and a 12-inch wafer with a resist film (film thickness 0.5 μm) was prepared by exposing the wafer to light (50 mJ) and heating (220°C) to dryness. The resist film was then removed by ashing using plasma gas under the following conditions. The wafer was then cleaned using each of the treatment solutions (treatment solutions 101 to 107) shown in Table 5 to remove the residue left after ashing removal (ashing residue). The number of defects on the cleaned wafer was then counted using an SP-2 (manufactured by KLA TENCOL) to evaluate the rinsing performance of each treatment solution on the ashing residue. [Conditions for removing ashing] Wafer temperature: 250℃ O2 gas flow rate: 1,000 sccm Pressure: 70Pa, Microwave output: 1kW -Evaluation criteria- AA: The number of defects was 50 or less. A: The number of defects was more than 50 but less than 80. B: The number of defects was more than 80 but less than 100. C: The number of defects was more than 100 but less than 150. D: The number of defects exceeds 150.

[0580] [Rinse performance after p-CMP] The surface of a 12-inch diameter Sematec 845 (copper wiring, TaN barrier metal, TEOS oxide film; Sematec) was polished and planarized using CSL9044C (slurry manufactured by FFPS). Then, a final polishing was performed using BSL8178C (slurry manufactured by FFPS). After cleaning with Clean100 (Wako Pure Chemical Industries), each processing solution was used as a rinse. Then, a pattern defect inspection system (ComPLUS manufactured by AMAT) was used to count the number of defects on the Sematec 844 pattern. The results were evaluated according to the following criteria.

[0581] -Evaluation criteria- AA: The number of defects was 50 or less. A: The number of defects was more than 50 but less than 80. B: The number of defects was more than 80 but less than 100. C: The number of defects was more than 100 but less than 150. D: The number of defects exceeds 150.

[0582] [Table 5]

Claims

1. one compound (A) selected from butyl acetate, 1-hexanol, 4-methyl-2-pentanol, propylene glycol monomethyl ether acetate, isopropanol, cyclohexanone, propylene glycol monomethyl ether, and methyl 3-methoxypropionate; One or more compounds (B) that satisfy any one of the following requirements (i) to (viii): One or more inorganic substances (C) containing any element selected from Al, B, S, N and K A processing solution for semiconductor manufacturing, which is any one selected from a developer, a rinse solution, a pre-wet solution, and a stripper solution, the content of compound (A) in the treatment liquid is 99.99 to 99.9999999% by mass, The content of the compound (B) in the treatment liquid is 10 －１１ % by mass or less, and the total content of the compound (B) in the treatment liquid is 10 －１０ up to 0.1% by mass, the content of each of the one or more inorganic substances (C) in the treatment liquid is 0.0001 to 100 ppb by mass, The ratio P of the compound (B) represented by the following formula I to the inorganic substance (C) is 10 ３ ~10 －６ and A processing solution for semiconductor manufacturing, having a total content of metal particles measured by SNP-ICP-MS of 0.001 to 100 mass ppt. P = [total mass of inorganic substance (C)] / [total mass of compound (B)] Formula I Requirement (i): When compound (A) is butyl acetate, compound (B) is the following compounds (b1) and (b2). Requirement (ii): When compound (A) is 1-hexanol, compound (B) is the following compounds (b3) and (b4). Requirement (iii): When compound (A) is 4-methyl-2-pentanol, compound (B) is the following compounds (b5) and (b6). Requirement (iv): When the compound (A) is propylene glycol monomethyl ether acetate, the compound (B) is the following compounds (b7) and (b8). Requirement (v): When compound (A) is isopropanol, compound (B) is the following compound (b9). Requirement (vi): When the compound (A) is cyclohexanone, the compound (B) is the following compounds (b10), (b11) and (b12). Requirement (vii): When the compound (A) is propylene glycol monomethyl ether, the compound (B) is the following compounds (b13) and (b14). Requirement (viii): When compound (A) is methyl 3-methoxypropionate, compound (B) is the following compounds (b15) and (b16). 【Chemistry 1】

2. 2. The processing solution for semiconductor manufacturing according to claim 1, wherein the inorganic substance (C) is a compound containing any element selected from the group consisting of Al, B, and S.

3. 3. The processing solution for semiconductor manufacturing according to claim 1, wherein the content of each of the one or more inorganic substances (C) contained in the processing solution for semiconductor manufacturing is 0.001 to 100 ppb by mass.

4. 4. The processing solution for semiconductor manufacturing according to claim 1, which contains Na, Ca, and Fe, and the content of each element is 0.01 ppt by mass to 1000 ppb by mass.

5. 5. The processing solution for semiconductor manufacturing according to claim 1, wherein the total content of metal particles measured by SNP-ICP-MS is 1 to 100 ppt by mass.

6. The ratio Q of the compound (A) and the compound (B) represented by the following formula II is 10 ４ ~10 １０ The processing solution for semiconductor manufacturing according to any one of claims 1 to 5, wherein Q = [total mass of compound (A)] / [total mass of compound (B)] Formula II

7. The processing solution for semiconductor manufacturing according to any one of claims 1 to 6, wherein the processing solution for semiconductor manufacturing is a developer.

8. 7. The processing solution for semiconductor manufacturing according to claim 1, wherein the processing solution for semiconductor manufacturing is a rinse solution.

9. 7. The processing solution for semiconductor manufacturing according to claim 1, wherein the processing solution for semiconductor manufacturing is a pre-wet solution.

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