Processing liquid for semiconductor manufacturing

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 a processing liquid for semiconductor manufacturing used in the manufacturing process of semiconductor devices, such as a developer, a rinse liquid, a pre-wet liquid, and a stripping liquid, a method for manufacturing the same, a pattern forming method, and a method for manufacturing an electronic device.

Background Art

[0002] The manufacturing process of semiconductor devices includes various processes such as a lithography process, an etching process, an ion implantation process, and a stripping process. Therefore, generally, after the completion of each process or before moving to the next process, a process of treating unnecessary organic and inorganic substances using a processing liquid is included. For example, a development process of treating an exposed resist film using a developer, a stripping process of treating the resist remaining on the substrate surface after substrate processing using a stripping liquid, and a rinsing process of further purifying the surface using a rinse liquid after the stripping process or the development process are included.

[0003] Such various processing liquids such as a developer, a rinse liquid, a pre-wet liquid, and a stripping liquid used in the manufacturing process of semiconductor devices (hereinafter also referred to as "processing liquid for semiconductor manufacturing", etc.) are required to be of high purity. As semiconductor miniaturization and high functionality progress, the market needs for high-purity processing liquids in general are increasing, and market expansion is expected in the future.

[0004] For a processing liquid for semiconductor manufacturing to be of high purity, it is a basic requirement that it has a low metal concentration and a low particle concentration. For example, Japanese Patent Application Laid-Open No. 2015-84122 discloses a technique capable of reducing particle generation in an organic developing solution. Also, metals in the processing liquid cause a phenomenon called migration where the metal diffuses into the target material during the processing. Migration inhibits the transmission of electrical signals and causes defects such as shorts. Moreover, not only that, but the metal itself can become dust that remains as a residue after processing, which can deteriorate the lithography performance, cause defects, and have an adverse effect on the formation of fine resist patterns or semiconductor elements. Against this background, there is a strong demand for further purification of the processing liquid for semiconductor manufacturing.

Summary of the Invention

Problems to be Solved by the Invention

[0005] In the current semiconductor manufacturing industry, the processing liquid for semiconductor manufacturing being used, especially the most advanced ones, has achieved a fairly high purity. For example, a rinse liquid using isopropanol (IPA) from FEUS, which boasts high purity and low metals, has a total metal concentration of several tens to several hundreds of mass ppt (parts per trillion). However, the performance required in the future, for example, has a metal concentration level of 10 ppt or less, and the current performance cannot meet this requirement.

[0006] Under such circumstances, the present invention has been developed. An object of the present invention is to provide a processing liquid for semiconductor manufacturing that suppresses deterioration of lithography performance and occurrence of defects and enables the manufacture of fine resist patterns or fine semiconductor elements. Another object of the present invention is to provide a method for manufacturing the processing liquid for semiconductor manufacturing. The present invention also aims to provide a pattern formation method using the above-mentioned processing liquid for semiconductor manufacturing and a method for manufacturing a semiconductor element including the pattern formation method.

Means for Solving the Problems

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

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

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

[0010] [5] A processing liquid for semiconductor manufacturing, containing Na, Ca and Fe, with the content ratio of each atom being 0.01 mass ppt to 1000 mass ppb, as described in any one of [1] to [4].

[0011] [6] A processing liquid for semiconductor manufacturing, as described in any one of [1] to [5], wherein the total content ratio of metal particles measured by the SNP-ICP-MS method is 0.001 to 100 mass ppt.

[0012] [7] A processing liquid for semiconductor manufacturing, as described in any one of [1] to [6], wherein the total content ratio of metal particles measured by the SNP-ICP-MS method is 1 to 100 mass ppt.

[0013] [8] A processing liquid for semiconductor manufacturing, as described in any one of [1] to [7], containing at least one compound represented by the following formulas I to V as the compound (B).

[0014]

Chemical formula

[0015] In formula I, R 1 and R 2 each independently represents an alkyl group or a cycloalkyl group, or are bonded to each other to form a ring. In formula II, R 3 and R 4 each independently represents 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. However, both R 3 and R 4 are not hydrogen atoms at the same time. In formula III, R 5 represents an alkyl group or a cycloalkyl group. In formula IV, R 6 and R 7 each independently represents an alkyl group or a cycloalkyl group, or are bonded to each other to form a ring. In formula V, R 8 and R 9 each independently represents an alkyl group or a cycloalkyl group, or are bonded to each other to form a ring. L represents a single bond or an alkylene group.

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

[10] A processing liquid for semiconductor manufacturing containing two or more of the processing liquids for semiconductor manufacturing according to any one of [1] to [9].

[0017]

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

[10] , wherein the processing liquid 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-wet liquid.

[0020]

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

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

[0021]

[15] A step of applying a photo-sensitive or radiation-sensitive resin composition to a substrate to form a photo-sensitive or radiation-sensitive film. The step of exposing the photosensitive ray or radiation-sensitive film, and The step of treating the substrate or the photosensitive ray or radiation-sensitive film with the treatment liquid for semiconductor manufacturing according to any one of [1] to

[13] , A pattern forming method including

[0022]

[16] As the step of treating the substrate or the photosensitive ray or radiation-sensitive film with the treatment liquid for semiconductor manufacturing, at least including the step of developing the photosensitive ray or radiation-sensitive film using the treatment liquid for semiconductor manufacturing as a developer, the pattern forming method according to

[15] .

[0023]

[17] As the step of treating the substrate or the photosensitive ray or radiation-sensitive film with the treatment liquid for semiconductor manufacturing, at least including the step of washing the photosensitive ray or radiation-sensitive film using the treatment liquid for semiconductor manufacturing as a rinse liquid, the pattern forming method according to

[15] or

[16] .

[0024]

[18] As the step of treating the substrate or the photosensitive ray or radiation-sensitive film with the treatment liquid for semiconductor manufacturing, at least including the step of treating the substrate using the treatment liquid for semiconductor manufacturing as a pre-wet liquid, the pattern forming method according to any one of

[15] to

[17] .

[0025]

[19] Using, as the treatment liquid for semiconductor manufacturing, a treatment liquid for semiconductor manufacturing having a dissolution rate at 23 °C of 0.0016 to 0.33 nm / second when the photosensitive ray or radiation-sensitive film before exposure is immersed, the pattern forming method according to any one of

[15] to

[18] .

[0026]

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

[15] to

[19] . [Advantages of the Invention]

[0027] According to the present invention, it has become possible to provide a processing liquid for semiconductor manufacturing that suppresses deterioration of lithography performance and occurrence of defects and enables the manufacture of fine resist patterns or fine semiconductor elements, and also to provide a method for manufacturing the processing liquid for semiconductor manufacturing. Further, according to the present invention, it has become possible to provide a pattern formation method using the above-described processing liquid for semiconductor manufacturing and a method for manufacturing a semiconductor element including the pattern formation method.

Brief Description of Drawings

[0028]

Figure 1

Figure 2

[0029] In the notation of a group (atomic group) in this specification, a notation that does not describe substitution and non-substitution includes both those having no substituent and those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

[0030] Further, the “actinic ray” or “radiation” in this specification means, for example, a spectral line of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet (EUV) rays, X-rays, or an electron beam (EB). Further, “light” in the present invention means actinic rays or radiation.

[0031] Further, the “exposure” in this specification includes not only exposure by far ultraviolet rays, X-rays, EUV light, etc. typified by a mercury lamp and an excimer laser but also drawing by particle beams such as an electron beam and an ion beam, unless otherwise specified.

[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". Further, the numerical range represented by "~" in this specification means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. Hereinafter, embodiments of the present invention will be described in detail.

[0033] <Processing liquid for semiconductor manufacturing> In the present invention, the "processing liquid for semiconductor manufacturing" is, as described above, a processing liquid used for treating organic substances after the completion of each step or before moving to the next step in the manufacturing process of semiconductor devices including lithography processes, etching processes, ion implantation processes, stripping processes, etc. Specifically, it is a processing liquid used as a developer, rinse liquid, pre-wet liquid, stripping liquid, etc.

[0034] The processing liquid for semiconductor manufacturing of the present invention (hereinafter also referred to as "the processing liquid of the present invention", etc.) contains one kind of compound (A) that satisfies the following requirement (a), at least one kind of compound (B) that satisfies the following requirement (b), and at least one kind of inorganic substance (C) having any element selected from Al, B, S, N, and K. Requirement (a): A compound selected from an alcohol compound, a ketone compound, and an ester compound, and having a content rate in the processing liquid of the present invention of 90.0 to 99.9999999 mass%. Requirement (b): A compound selected from an alcohol compound having 6 or more carbon atoms, a ketone compound, an ester compound, an ether compound, and an aldehyde compound, and having a content rate in the processing liquid of the present invention of 10 -11 ~0.1 mass%.

[0035] Compound (A) is the main component contained in the processing liquid of the present invention at a content rate of 90.0 to 99.9999999 mass%. The content rate is preferably, for example, 99.999 to 99.9999999 mass%, and particularly preferably 99.9999 to 99.9999999 mass%.

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

[0037] In the treatment liquid of the present invention, compound (B) is contained as an impurity, and the total content thereof is 10 -10 to 0.1% by mass based on the total mass of the treatment liquid. Here, the total content of compound (B) means the content described in requirement (b), that is, when there is one kind of compound (B) in the treatment liquid within the range of 10 -11 to 0.1% by mass, it means the content of this one kind of compound (B). When there are two or more kinds of compound (B) that satisfy the content requirement described in requirement (b), it means the total content of these two or more kinds of compound (B).

[0038] The content of compound (B) described in requirement (b) is preferably 10 -10 to 10 -4 % by mass, and more preferably 10 -10 to 10 -5 % by 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 during the synthesis of the treatment liquid of the present invention and mainly comes from the catalyst. In one form, the treatment liquid of the present invention contains, as the inorganic substance (C), a compound containing any element selected from Al, B, and S.

[0040] Compound (B) and the inorganic substance (C) are mostly removed in the purification step of the treatment liquid, but remain slightly in the purified treatment liquid.

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

[0042] P = [total mass of inorganic substance (C)] / [total mass of compound (B)] Formula I When the ratio P of inorganic substance (C) to compound (B) is 10 3 ~10 -6 In this range, deterioration of lithography performance and generation of defects can be suppressed, and it becomes possible to provide a fine resist pattern or a fine semiconductor element. Although the mechanism of this phenomenon is not necessarily clear, if the balance between compound (B) and inorganic substance (C) contained in the processing liquid is disrupted, for example, during processing with each processing liquid such as a developer, a rinse liquid, a pre-wet liquid, a stripping liquid, etc., it is presumed that a specific development that causes deterioration of lithography performance and generation of defects occurs.

[0043] The P value represented by formula I, which is the ratio of inorganic substance (C) to compound (B), is 10 3 ~10 -5 It is preferably, and more preferably 10 2 ~10 -4 As described above, compound (B) is an impurity contained slightly in the range of 10

[0044] ~0.1% by mass in total with respect to the total mass of the processing liquid, but the ratio Q of compound (A) to compound (B) represented by the following formula II is 10 -10 ~10 4 ~10 10 This is preferable from the viewpoints 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 that phenomenon is not clear, it has been confirmed that when the ratio Q of compound (A) to compound (B) is in the above range, the effect of the present invention is further improved.

[0046] The Q value represented by Formula II, which is the ratio of Compound (A) to Compound (B), is 10 5 ~10 10 is more preferably, 10 6 ~10 10 is even more preferably.

[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), 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 kinds of inorganic substances (C), the content of each inorganic substance (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, these compounds can remain on the substrate as nuclei of residual components during treatment, suppressing the cause of defects.

[0049] On the other hand, although it is generally considered that the less inorganic substance (C) there is, the more preferable it is, when it becomes less than 0.001 mass ppb, it has been confirmed that the defects tend to increase again. The mechanism is not necessarily clear, but when the inorganic substance (C) is removed from the substrate, it is presumed that it is removed in the form of a certain amount of ions or lumps of compounds, involving Compound (B). Therefore, when the inorganic substance (C) is too little, the removal rate of the inorganic substance (C) and Compound (B) deteriorates, and it is considered that they remain on the substrate and cause defects.

[0050] As described above, the Compound (A) contained in the treatment liquid of the present invention is a compound selected from an alcohol compound, a ketone compound, and an ester compound, and the treatment liquid of the present invention contains one or more of these compounds.

[0051] Examples of the alcohol compound include alcohols (monohydric alcohols) such as 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, 3-methoxy-1-butanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, and glycol ether solvents containing a hydroxyl group such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol), diethylene glycol monomethyl ether, methoxymethyl butanol, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, etc.

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

[0053] Examples of the ester compound include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isopropyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, and the like.

[0054] In one form, compound (A) may be a mixture of compounds having the same number of carbon atoms but different structures such as isomers. Only one kind of the compounds having the same number of carbon atoms but different structures may be included, or a plurality of kinds may be included as described above.

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

[0056] As described above, 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 of compound (B) is preferably 6 to 12, and more preferably 6 to 10.

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

[0058] [Chemical formula]

[0059] In formula I, R 1 and R 2 each independently represents an alkyl group or a cycloalkyl group, or are bonded to each other to form a ring.

[0060] R 1 and R 2 Examples of the alkyl group and cycloalkyl group represented by R

[0061] and R 1 and R 2 are preferably an alkyl group having 1 to 12 carbon atoms and a cycloalkyl group having 6 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms and a cycloalkyl group having 6 to 8 carbon atoms. The ring formed by R 1 and R 2 is a lactone ring, more preferably a 4- to 9-membered lactone ring, and even more preferably a 4- to 6-membered lactone ring. Note that R

[0062] In formula II, R 3 and R 4 each independently represents 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. However, both R 3 and R 4 are not hydrogen atoms.

[0063] R 3 and R 4 Examples of the alkyl group represented by R

[0064] R 3 and R 4Examples of the alkenyl group represented by [the formula] include an alkenyl group having 2 to 12 carbon atoms, preferably an alkenyl group having 2 to 8 carbon atoms.

[0065] R 3 and R 4 Examples of the cycloalkyl group represented by [the formula] include a cycloalkyl group having 6 to 12 carbon atoms, preferably a cycloalkyl group having 6 to 8 carbon atoms.

[0066] R 3 and R 4 Examples of the cycloalkenyl group represented by [the formula] include a cycloalkenyl group having 3 to 12 carbon atoms, preferably a cycloalkenyl group having 6 to 8 carbon atoms.

[0067] R 3 and R 4 The ring formed by the bonding of R and R 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. Note that R 3 and R 4 satisfy the relationship that the number of carbon atoms of the compound represented by formula II is 6 or more.

[0068] In formula III, R 5 represents an alkyl group or a cycloalkyl group. R 5 The alkyl group represented by [the formula] is an alkyl group having 6 or more carbon atoms, preferably an alkyl group having 6 to 12 carbon atoms, 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] R 5 The cycloalkyl group represented by [the formula] is a cycloalkyl group having 6 or more carbon atoms, preferably a cycloalkyl group having 6 to 12 carbon atoms, more preferably a cycloalkyl group having 6 to 10 carbon atoms.

[0070] In formula IV, R 6 and R 7 each independently represents an alkyl group or a cycloalkyl group, or are bonded to each other to form a ring.

[0071] R 6 and R 7 Examples of the alkyl group represented by

[0072] R 6 and R 7 are preferably alkyl groups having 1 to 12 carbon atoms, and more preferably alkyl groups having 1 to 8 carbon atoms.

[0073] R 6 and R 7 The ring formed by bonding to each other is a cyclic ether structure. This cyclic ether structure is preferably a 4- to 8-membered ring, and more preferably a 5- to 7-membered ring.

[0074] In addition, R 6 and R 7 satisfy the relationship that the number of carbon atoms in the compound represented by formula IV is 6 or more.

[0075] In formula V, R 8 and R 9 each independently represents an alkyl group, a cycloalkyl group, or are bonded to each other to form a ring. L represents a single bond or an alkylene group.

[0076] R 8 and R 9 Examples of the alkyl group represented by

[0077] R 8 and R 9 are preferably cycloalkyl groups having 6 to 12 carbon atoms, and more preferably cycloalkyl groups having 6 to 10 carbon atoms.

[0078] R 8 and R 9 The ring formed by the bonding of R and R is a cyclic diketone structure. This cyclic diketone structure is preferably a 6- to 12-membered ring, more preferably a 6- to 10-membered ring.

[0079] As the alkylene group represented by L, for example, an alkylene group having 1 to 12 carbon atoms is preferable, and an alkylene group having 1 to 10 carbon atoms is more preferable. In addition, R 8 , R 9 and L satisfy the relationship that the number of carbon atoms of the compound represented by Formula V is 6 or more. Specific examples of the compound (B) include, for example, the following compounds.

[0080]

Chemical formula

[0081] In one aspect, the treatment liquid of the present invention contains Na, Ca, and Fe, and the content ratio of each atom is preferably in the range of 0.01 mass ppt to 1000 mass ppb. Na, Ca, and Fe are metal atoms mixed in from various processes until the treatment liquid of the present invention is synthesized. When the concentration of each of these metal atoms is 1000 mass ppb or less, it is possible to suppress these metal atoms from remaining on the substrate as nuclei of residual components and causing defects.

[0082] On the other hand, although it is generally considered that the fewer these metal atoms are, the better, when it is less than 0.01 mass ppt, it has been confirmed that the defects tend to increase again. The mechanism is not clear, but when Na, Ca, or Fe is removed from the substrate, it is presumed that they are removed in the form of a certain amount of atomic mass, involving the compound (B) and / or the compound (C). Therefore, when Na, Ca, or Fe is too little, the removal rate of the compound (B) and / or the compound (C) and Na, Ca, or Fe deteriorates, and it is considered that they remain on the substrate and cause defects.

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

[0084] In one aspect, the treatment liquid of the present invention preferably has a total content ratio of metal particles, when measured by the SNP-ICP-MS method (Single-Particle ICP-MS), of 0.001 to 100 mass ppt, more preferably 1 to 100 mass ppt, based on the total mass of the treatment liquid of the present invention.

[0085] Metal atoms contained as impurities in the treatment liquid for semiconductor manufacturing are one of the factors causing defects in fine patterns and fine semiconductor elements. For this reason, it has been considered that the smaller the amount of metal atoms contained in the treatment liquid for semiconductor manufacturing, the better. However, the present inventor has found that the amount of metal atoms contained in the treatment liquid does not necessarily correlate with the defect generation rate, and there is variation in the defect generation rate.

[0086] By the way, according to the recently developed SNP-ICP-MS measurement, it has become possible to measure the amount of metal atoms present in a solution by separating them into 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] Hitherto, the amount of metal atoms contained in a treatment liquid for semiconductor manufacturing or the like has usually been analyzed by the ICP-MS method or the like. With conventional methods such as the ICP-MS method, since it is impossible to distinguish between ionic metals and metal particles (non-ionic metals) derived from metal atoms, the total mass of metal atoms, that is, the total mass of ionic metals and particulate metals (non-ionic metals) (hereinafter, also referred to as "total metal amount", etc.) is quantified.

[0088] The present inventors have intensively studied the effects of ionic metals and metal particles (non-ionic metals) derived from metal atoms contained in the treatment liquid, which can be identified and quantified by measurement using the SNP-ICP-MS method, on defects. As a result, it has been found that the amount of metal particles (non-ionic metals) has an extremely large effect on defect generation, and there is a correlation between the amount of metal particles (non-ionic metals) and defect generation.

[0089] In the treatment liquid of the present invention, the total content ratio of metal particles when measured by the SNP-ICP-MS method is particularly preferably 1 to 50 mass ppt. As an apparatus that can be used in the measurement using the SNP-ICP-MS method, in addition to the apparatus (NexION350S manufactured by PerkinElmer) used in the examples described later, for example, Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200) manufactured by Agilent Technologies; Agilent 8900 manufactured by Agilent Technologies, etc. can be mentioned.

[0090] In the embodiments 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 applications.

[0091] <Manufacture, etc. of treatment liquid for semiconductor manufacturing> The treatment liquid of the present invention can be produced by a known method. For example, a raw material is reacted in the presence of a catalyst to synthesize a compound (A), a crude liquid containing the compound (A) is obtained, and then this crude liquid is purified by, for example, filtering described later, etc.

[0092] The catalyst can be appropriately selected according to the compound (A). For example, sulfuric acid, HgSO 4 , NaNH 2 , Al(C 2 H 5 ) 3 , Ipc 2Examples include BH (Diisopinocampheylborane), a solid catalyst containing copper oxide - zinc oxide, a supported phosphoric acid catalyst, a supported copper catalyst, etc.

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

[0094] In the production of the treatment liquid of the present invention, it is preferable to use raw materials that have been purified in advance by distillation, ion exchange, filtration, etc. For example, those with a purity of 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 and use them. Using such high - purity raw materials is important for obtaining remarkable effects according to the present invention.

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

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

[0097] 〔Production Apparatus〕 FIG. 1 is a schematic diagram showing one form of a manufacturing apparatus that can be used in the method for manufacturing a processing liquid according to an embodiment of the present invention. The manufacturing apparatus 100 includes a tank 101, and the tank 101 is provided with a supply port 102 for supplying a cleaning liquid and / or an organic solvent (crude liquid containing compound (A)) described later. The manufacturing apparatus 100 includes a filtration device 105, and the tank 101 and the filtration device 105 are connected by a supply pipeline 109 so that a fluid (cleaning liquid, organic solvent, processing liquid, etc.) can be transferred between the tank 101 and the filtration device 105. A valve 103 and a pump 104 are arranged in the supply pipeline 109. In FIG. 1, the manufacturing apparatus 100 includes a tank 101 and a filtration device 105, but the manufacturing apparatus that can be used in the method for manufacturing a processing liquid according to an embodiment of the present invention is not limited to this.

[0098] In the manufacturing apparatus 100, the fluid supplied from the supply port 102 flows into the filtration device 105 through the valve 103 and the pump 104. The fluid discharged from the filtration device 105 is accommodated in the tank 101 through the circulation pipeline 110. The manufacturing apparatus 100 includes a discharge unit 111 for discharging the processing liquid into the circulation pipeline 110. The discharge unit 111 includes a valve 107 and a container 108, and can accommodate the manufactured processing liquid in the container 108 by switching the valve 106 provided in the circulation pipeline and the above-mentioned valve 107. In addition, a switchable pipeline 113 is connected to the valve 107, and the cleaning liquid after circulation cleaning can be discharged outside the manufacturing apparatus 100 through this pipeline 113. The cleaning liquid after circulation cleaning may contain particles, metal impurities, etc. According to the manufacturing apparatus 100 provided with the pipeline 113 for discharging the cleaning liquid outside the apparatus, the filling part of the container 108, etc. can be prevented from being contaminated, and a processing liquid having more excellent defect suppression performance can be obtained.

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

[0100] FIG. 2 is a schematic diagram showing another form of the manufacturing apparatus that can be used in the method for manufacturing a processing liquid according to the embodiment of the present invention. The manufacturing apparatus 200 includes a tank 101 and a filtering device 105, and further includes a distillation column 201 connected to the tank 101 by pipelines 202, 204, and 203 and arranged so that fluid can be transferred between the tank 101 through each of the above pipelines. On the other hand, as the manufacturing apparatus that can be used in the method for manufacturing a processing liquid according to the embodiment of the present invention, it is not necessarily required to include the filtering device 105 and / or the distillation column 201. On the other hand, further, a reaction vessel or the like connected to the distillation column 201 by the pipeline 203 may be provided.

[0101] In the manufacturing apparatus 200, the fluid supplied to the distillation column 201 through the pipeline 203 is distilled in the distillation column 201. The distilled fluid passes through the pipeline 202 and is stored in the tank 101. The supply pipeline 109 is provided with a valve 103 and a valve 206, and by switching with the valve 205 provided in the pipeline 204, the fluid discharged from the tank 101 can flow into the filtering device 105. In the manufacturing apparatus 200, the fluid discharged from the tank 101 can also flow back into the distillation column 201. In that case, by switching the above valves 103, 206, and 205, the fluid flows from the pipeline 204 into the distillation column 201 via the valve 207 and the pipeline 203.

[0102] The material of the liquid contact part of the manufacturing apparatus (the definition of the liquid contact part will be described later) is not particularly limited, but in terms of obtaining a treatment liquid with more excellent defect suppression performance, it is preferably formed from at least one selected from the group consisting of non-metallic materials and electrolytically polished metallic materials. In this specification, the "liquid contact part" refers to a part where the fluid may come into contact (for example, the inner surface of the tank, the liquid feed pump, the damper, the packing, the O-ring, and the inner surface of the pipeline, etc.), and intends a region with a thickness of 100 nm from its 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 less elution of metal atoms.

[0104] Examples of the fluorine-containing resin include perfluoro resins, such as tetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), tetrafluoroethylene-ethylene copolymer resin (ETFE), chlorotrifluoroethylene-ethylene copolymer resin (ECTFE), vinylidene fluoride resin (PVDF), chlorotrifluoroethylene copolymer resin (PCTFE), vinyl fluoride resin (PVF), etc.

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

[0106] The above-mentioned metal material is not particularly limited, and known materials can be used. Examples of the metal material include a metal material in which the total content of chromium and nickel exceeds 25% by mass based on the total mass of the metal material. Among them, 30% by mass or more is more preferable. The upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but generally 90% by mass or less is preferable. Examples of the metal material 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 steel can be used. Among them, an alloy containing 8% by mass or more of nickel is preferable, and an austenitic stainless steel containing 8% by mass or more of nickel is more preferable. Examples of the 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 known nickel-chromium alloys can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75% by mass and a chromium content of 1 to 30% by mass is preferable.

[0109] Examples of the nickel-chromium alloy include Hastelloy (trade name, the same hereinafter), Monel (trade name, the same hereinafter), and Inconel (trade name, the same hereinafter). More specifically, Hastelloy C-276 (Ni content 63% by mass, Cr content 16% by mass), Hastelloy-C (Ni content 60% by mass, Cr content 17% by mass), Hastelloy C-22 (Ni content 61% by mass, Cr content 22% by mass), etc. can be mentioned. In addition, the nickel-chromium alloy may further contain boron, silicon, tungsten, molybdenum, copper, cobalt, etc. in addition to the above-described alloy, if necessary.

[0110] The method for electrolytic polishing the metal material is not particularly limited, and a known method can be used. For example, the methods described in paragraphs 0011 to 0014 of JP-A-2015-227501 and paragraphs 0036 to 0042 of JP-A-2008-264929 can be used.

[0111] It is presumed that the chromium content in the passive layer on the surface of the metal material becomes higher than the chromium content in the matrix phase by electrolytic polishing. Therefore, it is presumed that from the distillation column formed of the metal material whose liquid contact part is electrolytically polished, it is possible to obtain a distilled organic solvent with a reduced impurity content because metal impurities containing metal atoms in the organic solvent hardly flow out. The metal material may be buffed. The method of buffing is not particularly limited, and a known method can be used. The size of the abrasive grains used for the finish of buffing is not particularly limited, but #400 or less is preferable in that the unevenness on the surface of the metal material is more likely to become smaller. Note that buffing is preferably performed before electrolytic polishing.

[0112] In terms of obtaining a treatment liquid having more excellent defect suppression performance, the liquid contact part is preferably formed of electrolytically polished stainless steel. In particular, when the manufacturing apparatus includes a tank, it is more preferable that the liquid contact part of the tank is formed of electrolytically polished stainless steel. The content mass ratio of Cr to Fe in the liquid contact part (hereinafter, also referred to as "Cr / Fe") is not particularly limited, but generally, 0.5 to 4 is preferable, and in particular, in terms of making it more difficult for metal impurities and / or organic impurities to elute into the treatment liquid, more than 0.5 and less than 3.5 is more preferable, and 0.7 or more and 3.0 or less is more preferable. When Cr / Fe exceeds 0.5, elution of metal from inside the tank can be suppressed, and when Cr / Fe is less than 3.5, peeling of the liquid contact part that causes particles is less likely to occur. The method for adjusting Cr / Fe in the above 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 higher than the chromium content in the matrix phase by electrolytic polishing.

[0113] The above metal material may be a metal material to which a film technology is applied. The film technology is roughly classified into three types: metal coating (various platings), inorganic coating (various chemical conversion treatments, glass, concrete, ceramics, etc.), and organic coating (rust preventive oil, paint, rubber, plastics, etc.), and any of them may be used. Preferred film technologies include surface treatment with rust preventive oil, rust inhibitor, corrosion inhibitor, chelate compound, peelable plastic, and lining agent.

[0114] Among them, as the film technology, surface treatment with a corrosion inhibitor, a chelate compound, and a lining agent is preferable. Here, examples of the corrosion inhibitor include various chromates, nitrites, silicates, phosphates, carboxylic acids (oleic acid, dimer acid, naphthenic acid, etc.), metal soaps of carboxylic acids, sulfonates, amine salts, and esters (glycerol esters of higher fatty acids and phosphate esters). Examples of the chelate compound include ethylenediaminetetraacetic acid, gluconic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, and diethylenetriaminepentaacetic acid. Examples of the lining agent include fluororesin lining agents. Particularly preferred is treatment with a phosphate or a fluororesin lining agent.

[0115] By providing the filtration device 105, the above manufacturing apparatus can easily obtain a treatment liquid having more excellent defect suppression performance. The filtration member included in the filtration device 105 is not particularly limited, but at least one selected from the group consisting of a filter having a particle removal diameter of 20 nm or less and a metal ion adsorption filter is preferable, and it is more preferable that the filter has a particle removal diameter of 20 nm or less and is a metal ion adsorption filter.

[0116] · Filters with a particle removal diameter of 20 nm or less Filters with a particle removal diameter of 20 nm or less have the function of efficiently removing particles with a diameter of 20 nm or more from organic solvents and the like that are raw materials of the processing liquid. Note that the particle removal diameter of the filter is preferably 1 to 15 nm, more preferably 1 to 12 nm. When the particle removal diameter is 15 nm or less, finer particles can be removed, and when the particle removal diameter is 1 nm or more, the filtration efficiency is improved. Here, the particle removal diameter means the minimum size of particles that can be removed by the filter. For example, when the particle removal diameter of the filter is 20 nm, particles with a diameter of 20 nm or more can be removed.

[0117] Examples of the filter material include nylon 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. Regarding solvent resistance, fluororesin, polyimide, and / or polyamideimide are excellent. Also, from the viewpoint of adsorbing metal ions, nylon such as 6-nylon and 6,6-nylon is particularly preferable.

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

[0119] · Metal ion adsorption filter The above filtration device 105 preferably contains a metal ion adsorption filter. The metal ion adsorption filter is not particularly limited, and known metal ion adsorption filters can be mentioned.

[0120] Among them, as the metal ion adsorption filter, an ion-exchangeable filter is preferable. Here, the metal ions to be adsorbed are not particularly limited, but from the viewpoint that they are likely to cause defects in semiconductor devices, ions of a metal containing one selected from the group consisting of Fe, Cr, Ni, and Pb are preferable, and ions of metals containing Fe, Cr, Ni, and Pb respectively are preferable.

[0121] The metal ion adsorption filter preferably contains an acid group on its surface from the viewpoint of improving the adsorption performance of metal ions. Examples of the acid group include a sulfo group and a carboxy group.

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

[0123] Further, the metal ion adsorption filter may be composed 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, polyimide, and / or polyamideimide, it has better solvent resistance.

[0125] ·Organic impurity adsorption filter The filtration device 105 may further contain an organic impurity adsorption filter. The organic impurity adsorption filter is not particularly limited, and known organic impurity adsorption filters can be mentioned. Among them, as the organic impurity adsorption filter, in terms of improving the adsorption performance of organic impurities, it is preferable to have an organic skeleton capable of interacting with organic impurities on the surface (in other words, the surface is modified by an organic skeleton capable of interacting with organic impurities). Examples of the organic skeleton capable of interacting with organic impurities include chemical structures that can react with organic impurities to capture the organic impurities on the organic impurity adsorption filter. More specifically, when the organic impurity contains n-long-chain alkyl alcohol (a structural isomer when 1-long-chain alkyl alcohol is used as the organic solvent), the organic skeleton includes an alkyl group. When the organic impurity contains dibutylhydroxytoluene (BHT), the organic skeleton includes a phenyl group.

[0126] Examples of the base material (material) constituting the organic impurity adsorption filter include cellulose carrying activated carbon, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, and fluororesin.

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

[0128] As the organic impurity adsorption filter, in addition to the above-described chemisorption (adsorption using an organic impurity adsorption filter having an organic substance skeleton capable of interacting with an organic impurity on the surface), a physical adsorption method can also be applied.

[0129] For example, when BHT is included as an organic impurity, the structure of BHT is larger than 10 angstroms (= 1 nm). Therefore, by using an organic impurity adsorption filter having a pore diameter of 1 nm, BHT cannot pass through the pores of the filter. That is, BHT is physically captured by the filter and thus removed from the product to be purified. Thus, removal of organic impurities is possible not only by chemical interaction but also by applying a physical removal method. However, in this case, a filter having a pore diameter of 3 nm or more is used as a "particle removal filter", and a filter having a pore diameter of less than 3 nm is used as an "organic impurity adsorption filter".

[0130] Although it is repetitive, when using filters, different filters may be combined. In that case, the filtering with the first filter may be performed only once or may be performed two or more times. When filtering is performed two or more times by combining different filters, each filter may be of the same type as each other or may be of different types from each other, but it is preferable that they are of different types from each other. Typically, it is preferable that at least one of the pore diameter and the constituent material of the first filter and the second filter is different.

[0131] It is preferable that the pore diameter after the second time be the same as or smaller than the pore diameter of the first filtering. Also, first filters with different pore diameters may be combined within the above-described range. The pore diameter here can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, various filters provided by Nippon Pall Corporation, Advantec Toyo Co., Ltd., Nippon Integris Co., Ltd. (former Nippon Microlith Co., Ltd.) or Kits Microfilter Co., Ltd. can be selected. Also, "P-nylon filter (pore diameter 0.02 μm, critical surface tension 77 mN / m)" made of polyamide; (manufactured by Nippon Pall Corporation), "PE·Clean filter (pore diameter 0.02 μm)" made of high-density polyethylene; (manufactured by Nippon Pall Corporation), and "PE·Clean filter (pore diameter 0.01 μm)" made of high-density polyethylene; (manufactured by Nippon Pall Corporation) can also be used.

[0132] The method for manufacturing a processing liquid according to an embodiment of the present invention may include a step of cleaning a manufacturing apparatus using a cleaning liquid. The method supplies the cleaning liquid from the supply port 102 of the tank 101. The supply amount of the cleaning liquid is not particularly limited, but an amount sufficient to sufficiently clean the liquid contact portion of the tank 101 is preferable, and the volume of the cleaning liquid to be supplied is preferably 30% by volume or more with respect to the volume of the tank 101. When supplying the cleaning liquid from the supply port 102, the valve 103 may be closed or open, but in terms of making it easier to clean the tank 101, it is preferable to close the valve 103 when supplying the cleaning liquid from the supply port 102.

[0133] The cleaning liquid supplied to the tank 101 may be immediately transferred inside the manufacturing apparatus, or it may be transferred inside the manufacturing apparatus (for example, through the supply pipe 109) after cleaning the inside of the tank 101. The method for cleaning the inside of the tank 101 using the cleaning liquid is not particularly limited, and examples thereof include a method of rotating a stirring blade (not shown) provided in the tank 101 for cleaning. The time for cleaning the tank using the cleaning liquid is not particularly limited, and it may be appropriately selected according to the material of the liquid contact part of the tank 101, the type of the processing liquid to be manufactured, and the possibility of contamination, etc. Generally, about 0.1 seconds to 48 hours is preferable. When only the tank 101 is cleaned, for example, the cleaning liquid after cleaning may be discharged from a discharge port (not shown) provided at the bottom of the tank.

[0134] The method for cleaning the supply pipe 109 and the like of the manufacturing apparatus 100 using the cleaning liquid is not particularly limited, but a method of opening the valves 103 and 106, closing the valve 107, operating the pump 104, and circulating the cleaning liquid inside the manufacturing apparatus through the supply pipe 109 and the circulation pipe 110 (hereinafter, also referred to as "circulation cleaning") is preferable. By doing so, while transferring the cleaning liquid, foreign matters and the like adhering to the liquid contact parts such as the tank 101, the filtration device 105, and the supply pipe 109 can be efficiently dispersed in the cleaning liquid and / or dissolved more efficiently.

[0135] In particular, when the manufacturing apparatus includes a filtration device, circulation cleaning is more preferable as the cleaning method. An example of circulation cleaning will be described with reference to FIG. 1. First, the cleaning liquid supplied from the tank 101 into the manufacturing apparatus through the valve 103 returns (circulates) to the tank 101 again through the supply pipe 109 (through the filtration device 105, the circulation pipe 110, and the valve 106). At this time, the cleaning liquid is filtered by the filtration device 105, and particles and the like dissolved and dispersed in the cleaning liquid are removed, and the cleaning effect can be further enhanced.

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

[0137] (Cleaning liquid) The cleaning liquid used when cleaning in advance as described above is not particularly limited, and known cleaning liquids can be used.

[0138] Examples of the cleaning liquid include water, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, 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] Also, as the cleaning liquid, for example, those described in JP-A No. 2016-57614, JP-A No. 2014-219664, JP-A No. 2016-138219, and JP-A No. 2015-135379 may be used.

[0140] As the cleaning liquid, it is preferably contained at least one selected from the group consisting of 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 (isopropanol), MEK (methyl ethyl ketone), and MIBC (4-methyl-2-pentanol). More preferably, it 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. Even more preferably, it 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] Note that the cleaning liquid may be used alone or in combination of two or more. Also, the treatment liquid of the present invention may be used as the cleaning liquid.

[0142] [Method for adjusting metal content rate] In the treatment liquid of the present invention, the ion concentrations of Cr, Co, Cu, Pb, Li, Mg, Mn, Ni, K, Ag, and Zn are preferably all 1 ppm (parts per million) or less, more preferably 1 ppb or less. In particular, it is even more preferably on the order of ppt (the above concentrations are all based on mass), and particularly preferably substantially not contained.

[0143] The adjustment of the metal content in the treatment liquid of the present invention may be performed, for example, by repeating distillation, filter filtration, filtration using an ion exchange resin, adsorption purification, etc. at least one of the stages of the raw materials used in manufacturing the treatment liquid and the stage after preparing the treatment liquid, and purifying sufficiently.

[0144] Here, the method for adjusting the metal content (hereinafter, also referred to as "method for reducing the metal concentration") is not particularly limited, and examples include adsorption purification using silicon carbide described in International Publication No. WO12 / 043496 pamphlet. Further, examples of preferably combining distillation, filter filtration, and filtration using an ion exchange resin and purifying sufficiently are mentioned as preferred forms.

[0145] From the viewpoint of obtaining the effects of the present invention, the method for adjusting the metal content is particularly preferably carried out at the stage of the raw materials used in manufacturing the treatment liquid. Further, it is preferable to use raw materials of a grade with reduced specific metal atoms, inorganic ions such as sulfate ions, chloride ions, or nitrate ions, and metal ions described later.

[0146] As other methods related to the method for reducing the metal concentration, as the "container" for accommodating the raw materials used in manufacturing the treatment liquid, a container with little elution of impurities, as described in the description of the accommodation container for accommodating the treatment liquid of the present invention described later, can be used. Further, methods such as lining the inner wall of the pipe with a fluororesin so that metal components do not elute from the "pipe" etc. during the preparation of the treatment liquid are also mentioned.

[0147] [Impurities and Coarse Particles] Further, the treatment liquid of the present invention preferably does not substantially contain coarse particles. Note that the coarse particles contained in the treatment liquid are 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 brought in as contaminants during the preparation of the treatment liquid. Those that ultimately do not dissolve in the treatment liquid and exist as particles are applicable. The amount of coarse particles present in the treatment liquid can be measured in the liquid phase using a commercially available measuring device in a light scattering type in-liquid particle measurement method using a laser as a light source.

[0148] [Kit and Concentrate] The treatment liquid of the present invention may be in the form of a kit to which other raw materials are separately added. In this case, as other raw materials to be separately added during use, in addition to solvents such as water and organic solvents, other compounds can be mixed and used according to the application. From the viewpoint of significantly obtaining the effects of the present invention, when using a solvent that can be used at this time, if the content rate of each of Na, Ca, or Fe contained in the solvent is within the range of the specific values of the present invention described above, the desired effects of the present invention can be significantly obtained.

[0149] [Container] The treatment liquid of the present invention can be filled in any container for storage, transportation, and use as long as corrosiveness or the like is not a problem (regardless of whether it is a kit). As the container, for semiconductor applications, those with a high degree of cleanliness and low elution of impurities are preferred. Examples of usable containers include the "Clean Bottle" series manufactured by Asahi Kasei Chemicals Corporation and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd., but are not limited thereto.

[0150] The liquid contact part of the container is preferably formed of a non-metallic material or stainless steel. Examples of the non-metallic material include the materials exemplified as the non-metallic materials used for the liquid contact part of the distillation column described above. In particular, among these, when using a container in which the liquid contact part is a fluororesin, compared with the case of using a container in which the liquid contact part is a polyethylene resin, a polypropylene resin, or a polyethylene - polypropylene resin, the occurrence of problems such as elution of ethylene or propylene oligomers can be suppressed.

[0151] Specific examples of containers in which such a liquid contact part is made of a fluororesin include, for example, FluoroPure PFA composite drums manufactured by Entegris. In addition, containers described on page 4 of Japanese Patent Publication No. Hei 3-502677, page 3 of International Publication No. 2004 / 016526, pages 9 and 16 of International Publication No. 99 / 46309, etc. can also be used. When the liquid contact part is made of a non-metallic material, it is preferably such that elution into the non-metallic material is suppressed.

[0152] As the container, it is also preferable that the liquid contact part that comes into contact with the processing liquid is formed of stainless steel, and more preferably formed of electrolytically polished stainless steel.

[0153] When the above-mentioned container stores the processing liquid, impurity metals and / or organic impurities are less likely to elute into the processing liquid stored in the container.

[0154] The form of the above-mentioned stainless steel is as already described for the material of the liquid contact part of the distillation column. The same also applies to electrolytically polished stainless steel.

[0155] The Cr / Fe ratio in the stainless steel forming the liquid contact part of the above-mentioned container is as already described for the Cr / Fe ratio of the liquid contact part of the tank.

[0156] It is preferable to clean the inside of these containers before filling. The liquid used for cleaning is not particularly limited, but preferably has a metal content of less than 0.001 mass ppt (parts per trillion). Also, depending on the application, in addition to the water described later, other organic solvents purified to have a metal content within the above range, or the treatment liquid of the present invention itself, or a diluted treatment liquid of the present invention, or a liquid containing at least one of the compounds added to the treatment liquid of the present invention, the effects of the present invention can be significantly obtained.

[0157] After production, the above treatment liquid may be bottled in containers such as gallon bottles or coated bottles and then transported and stored. The gallon bottle may be made of glass material or other materials.

[0158] For the purpose of preventing changes in the components in the solution during storage, the inside of the container may be replaced with an inert gas (such as nitrogen or argon) with a purity of 99.99995% by volume or more. In particular, a gas with a low water content is preferred. Also, during transportation and storage, room temperature may be used, but for preventing deterioration, the temperature may be controlled in the range of -20°C to 30°C.

[0159] Also, before cleaning the container, it is preferable to remove foreign substances adhering to the lids of various containers by cleaning the lids with an acid or an organic solvent, etc., so as to prevent foreign substances from entering the container from the lids.

[0160] [Water] The water used in connection with the present invention, for example, the water that can be used in the production process of the treatment liquid of the present invention, the water that can be used in the pattern formation process of the present invention, the water that can be used for cleaning the storage container of the treatment liquid of the present invention, and the water that can be used for measuring the components of the treatment liquid of the present invention and for the measurement for evaluating the defect suppression performance and lithography performance related to the effects of the present invention, it is preferable to use ultrapure water used in semiconductor manufacturing. Further, it is more preferable to use water obtained by further purifying the ultrapure water to reduce inorganic anions, metal ions, etc. The purification method is not particularly limited, but purification using a filtration membrane or an ion exchange membrane, or purification by distillation is preferred. Also, for example, it is preferable to perform purification by the method described in JP-A-2007-254168.

[0161] In one form, it is preferable that the metal content of these waters is less than 0.001 mass ppt (parts per trillion).

[0162] [Clean room] It is preferable to perform all handling operations including the adjustment of the processing liquid of the present invention, the opening and / or cleaning of the storage container, the filling of the processing liquid, etc., as well as the processing analysis and measurement in a clean room. The clean room preferably meets the 14644-1 clean room standard. It is preferable to meet any one of ISO Class 1, ISO Class 2, ISO Class 3, and ISO Class 4, more preferably to meet ISO Class 1 or ISO Class 2, and particularly preferably to be ISO Class 1. 〔Use of the processing liquid〕 The processing liquid of the present invention is preferably used for semiconductor manufacturing. Specifically, in the manufacturing process of semiconductor devices containing lithography processes, etching processes, ion implantation processes, and stripping processes, etc., it is used to treat organic substances after the end of each process or before moving to the next process, and is specifically preferably used as a pre-wet liquid, developer, rinse liquid, and stripping liquid, etc. For example, it can also be used for rinsing the edge lines of semiconductor substrates before and after resist coating.

[0163] In addition, the above processing liquid can also be used as a cleaning liquid for devices for manufacturing various processing liquids used in semiconductor manufacturing.

[0164] In addition, the above processing liquid can also be used as a diluent for the resin contained in the resist liquid (described later). That is, it can also be used as a solvent contained in a photosensitive or radiation-sensitive composition. In addition, the above processing liquid can also be preferably used in other applications other than semiconductor manufacturing, and can also be used as a developer and rinse liquid for polyimide, resist for sensors, resist for lenses, etc.

[0165] In addition, the above processing liquid can also be used as a solvent for medical or cleaning applications. In particular, it can be preferably used for cleaning containers, pipes, and substrates (such as wafers and glass, etc.). <Pattern formation method> The processing liquid of the present invention is basically a processing liquid used as a developer, a rinse liquid, a pre-wet liquid, a stripping agent, etc. in a method for manufacturing a semiconductor device. In one aspect, in a pattern formation method included in a method for manufacturing a semiconductor device, it is preferably used as a developer, a rinse liquid, or a pre-wet liquid.

[0166] The pattern formation method of the present invention includes a resist film formation step of applying a radiation-sensitive or radiation-sensitive composition (hereinafter also referred to as a "resist composition") to a substrate to form a radiation-sensitive or radiation-sensitive film (hereinafter also referred to as a "resist film"), an exposure step of exposing the resist film, and a processing step of processing the substrate before applying the resist composition or the exposed resist film with the above-described processing liquid.

[0167] In the pattern formation method of the present invention, the processing liquid of the present invention may be used as any one of a developer, a rinse liquid, and a pre-wet liquid, preferably used as any two of a developer, a rinse liquid, and a pre-wet liquid, and more preferably used as a developer, a rinse liquid, and a pre-wet liquid.

[0168] Hereinafter, each step included in the pattern formation method of the present invention will be described. Further, as an example of the processing step using the processing liquid of the present invention, each of the pre-wet step, the development step, and the rinse step will be described.

[0169] <Pre-wet step> The pattern formation method of the present invention may include a pre-wet step of previously applying a pre-wet liquid onto a substrate in order to improve coatability before the step of forming a resist film using a radiation-sensitive or radiation-sensitive composition. For example, the pre-wet step is described in Japanese Patent Application Laid-Open No. 2014-220301, and these are incorporated herein by reference.

[0170] <Resist film formation step> The resist film formation step is a step of forming a resist film using a radiation-sensitive or radiation-sensitive composition, and can be performed, for example, by the following method.

[0171] In order to form a resist film (photosensitive or radiation-sensitive composition film) on a substrate using a photosensitive or radiation-sensitive composition, each component described below is dissolved in a solvent to prepare a photosensitive or radiation-sensitive composition, and after filtering through a filter if necessary, it is applied onto the substrate. As the filter, those 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 are preferred.

[0172] The photosensitive or radiation-sensitive composition is applied onto a substrate (e.g., silicon, silicon dioxide-coated) such as those used in the manufacture of integrated circuit elements by an appropriate coating method such as a spinner. Thereafter, it is dried to form a resist film. If necessary, various underlayer films (inorganic film, organic film, antireflection film) may be formed under the resist film.

[0173] As a drying method, a method of heating and drying is generally used. Heating can be carried out by means provided in a normal exposure and development machine, or it may be carried out using a hot plate or the like.

[0174] The heating temperature is preferably carried out at 80 to 180 °C, more preferably at 80 to 150 °C, even more preferably at 80 to 140 °C, and particularly preferably at 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 film thickness of the resist film is generally 200 nm or less, and preferably 100 nm or less. For example, in order to resolve a 1:1 line and space pattern with a size of 30 nm or less, the film thickness of the formed resist film is preferably 50 nm or less. If the film thickness is 50 nm or less, pattern collapse is less likely to occur when the development process described below is applied, and better resolution performance can be obtained.

[0176] The film thickness range 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 range is even more preferably 15 nm to 40 nm. When the film thickness is within this range, both etching resistance and better resolution performance can be satisfied simultaneously.

[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, for example, using a composition for forming an upper layer film containing a hydrophobic resin, an acid generator, and a basic compound. The upper layer film and the composition for forming the upper layer film are as described later.

[0178] <Exposure step> The exposure step is a step of exposing the resist film, and can be performed, 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, direct writing (without a mask) is generally used.

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

[0180] <Baking> In the pattern forming method of the present invention, it is preferable to perform baking (heating) after exposure and before development. Baking promotes the reaction in the exposed area, and the sensitivity and pattern shape become better. 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 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds. The heating can be performed by means provided in a normal exposure and development machine, or may be performed using a hot plate or the like.

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

[0182] As the development method, for example, a method of immersing a substrate in a tank filled with a developer for a certain period of time (dip method), a method of developing by raising the developer on the substrate surface by surface tension and allowing it to stand still for a certain period of time (paddle method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning a developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispense method), etc. can be applied. In addition, after the step of performing development, a step of stopping development while substituting with another solvent may be carried out.

[0183] The development time is not particularly limited as long as the resin in the unexposed portion is sufficiently dissolved, and is usually 10 to 300 seconds, preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C. As the developer used in the development process, it is preferable to use the above-described treatment liquid. Regarding the developer, it is as described above. In addition to development using the treatment liquid, development with an alkaline developer may be performed (so-called double development).

[0184] <Rinse process> The rinse process is a process of washing (rinsing) with a rinse liquid after the above-described development process. In the rinse process, the wafer on which development has been performed is subjected to a washing process using the above-described rinse liquid.

[0185] The method of the cleaning process is not particularly limited. For example, a method of continuously discharging a rinse liquid onto a substrate rotating at a constant speed (rotary discharge method), a method of immersing the substrate in a tank filled with the rinse liquid for a certain period of time (dip method), a method of spraying the rinse liquid onto the substrate surface (spray method), etc. can be applied. Among these, it is preferable to perform the cleaning process by the rotary discharge method, and after cleaning, rotate the substrate at a rotational speed of 2000 rpm to 4000 rpm to remove the rinse liquid from the substrate.

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

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

[0188] As the rinse liquid, it is preferable to use the above-described treatment liquid. The description of the rinse liquid is as described above.

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

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

[0191] Here, the dissolution rate of the photoactive or radiation-sensitive film with respect to the treatment liquid of the present invention is the rate of decrease in film thickness when the photoactive or radiation-sensitive film is immersed in the treatment liquid of the present invention after forming the film, and in the present invention, it is the dissolution rate at 23°C. This dissolution rate is more preferably 0.0016 to 0.16 nm / second, and even more preferably 0.0016 to 0.08 nm / second.

[0192] <Photoactive or Radiation-Sensitive Composition (Resist Composition)> Next, the photoactive or radiation-sensitive composition that is preferably used in combination with the treatment liquid of the present invention will be described in detail.

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

[0194] Note that when it has a repeating unit that decomposes 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 the acid.

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

[0196] [Chemical formula]

[0197] In the formula, R 41 , R 42 and R 43 each independently represent a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R 42 may be bonded to Ar 4 to form a ring, and in that case, R 42 represents a single bond or an alkylene group. X 4 represents a single bond, -COO-, or -CONR 64 -, and R 64 represents a hydrogen atom or an alkyl group. L 4 represents a single bond or an alkylene group. Ar 4 represents an (n + 1)-valent aromatic ring group, and when bonded to R 42 to form a ring, it represents an (n + 2)-valent aromatic ring group. n represents an integer from 1 to 5.

[0198] Examples of the alkyl group of R 41 , R 42 , and R 43 in the general formula (I) preferably include an alkyl group having 20 or fewer carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a dodecyl group, etc., which may have substituents, more preferably an alkyl group having 8 or fewer carbon atoms, and particularly preferably an alkyl group having 3 or fewer carbon atoms.

[0199] Examples of the alkyl group of R 41 , R 42 , and R 43The cycloalkyl group may be monocyclic or polycyclic. 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 optionally have a substituent.

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

[0201] R in the general formula (I) 41 , R 42 , R 43 The alkyl group contained in the alkoxycarbonyl group of, and, is preferably the same as the alkyl group in the above R 41 , R 42 , R 43 .

[0202] Preferred substituents in the above groups include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide 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, a nitro group, etc., and the carbon number of the substituent is preferably 8 or less.

[0203] Ar 4 represents an (n + 1)-valent aromatic ring group. When n is 1, the divalent aromatic ring group may have a substituent, and examples thereof include arylene groups having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, and an anthracenylene group, or aromatic ring groups containing a heterocycle, such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole, which are preferred examples.

[0204] When n is an integer of 2 or more, specific examples of the (n + 1)-valent aromatic ring group can preferably include groups formed by removing (n - 1) arbitrary hydrogen atoms from the above-described specific examples of the divalent aromatic ring group. The (n + 1)-valent aromatic ring group may further have a substituent.

[0205] Examples of the substituents that the above-described alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n + 1)-valent aromatic ring group may have include, for example, R in the general formula (I) 41 , R 42 , R 43 and the alkyl groups, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, butoxy group, and other alkoxy groups such as those exemplified; aryl groups such as phenyl group; and the like.

[0206] X 4 represented by -CONR 64 -(wherein R 64 represents a hydrogen atom or an alkyl group), the alkyl group of R 64 is preferably an alkyl group having 20 or fewer 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, dodecyl group, etc., which may have a substituent, and more preferably an alkyl group having 8 or fewer carbon atoms. X 4 is preferably a single bond, -COO-, -CONH-, and more preferably a single bond, -COO-.

[0207] L 4 The alkylene group in is preferably one having 1 to 8 carbon atoms, such as a methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, etc., which may have a substituent.

[0208] Ar 4 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, naphthalene ring group, biphenylene ring group.

[0209] The repeating unit represented by the general formula (I) preferably has a hydroxystyrene structure. That is, Ar 4 is preferably a benzene ring group.

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

[0211]

Chemical formula

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

[0213] Ar in the general formula (p1) represents an aromatic ring, for example, an aromatic hydrocarbon ring which may have a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, a phenanthrene ring, or, for example, a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, a thiazole ring, etc. Among them, a benzene ring is most preferred.

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

[0215] Hereinafter, specific examples of the repeating unit having a phenolic hydroxyl group in the resin (A) are shown, but the present invention is not limited thereto. In the formula, a represents 1 or 2.

[0216]

Chemical formula

[0217]

Chem.

[0218]

Chem.

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

[0220] The repeating unit having a group that decomposes by the action of the acid possessed by the resin (A) to generate a carboxyl group is a repeating unit having a group in which the hydrogen atom of the carboxyl group is substituted by a group that decomposes and dissociates by the action of the acid.

[0221] Examples of the group that dissociates with an acid include, for example, -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 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R 36 and R 37 may be bonded to each other to form a ring.

[0223] R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

[0224] As the repeating unit having a group that decomposes by the action of an acid to generate a carboxyl group in the resin (A), a repeating unit represented by the following general formula (AI) is preferable.

[0225]

Chemical formula

[0226] In the general formula (AI), Xa 1 represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group.

[0227] Rx 1 ~Rx 3 each independently represents an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx 1 ~Rx 3 are alkyl groups (linear or branched), it is preferable that at least two of Rx 1 ~Rx 3 are methyl groups. Rx 1 ~Rx 3 Two of them may combine to form a cycloalkyl group (monocyclic or polycyclic).

[0228] Xa 1 Examples of the alkyl group which may have a substituent and is represented by include a methyl group or a group represented by -CH 2 -R 11 . 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. Xa 1 is, in one aspect, preferably a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group or the like.

[0229] Examples of the divalent linking group of T include an alkylene group, a -COO-Rt- group, an -O-Rt- group, etc. In the formula, 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, -CH 2 - group, -(CH 2 ) 2 - group, -(CH 2 ) 3 - group is more preferred.

[0230] Rx 1 ~Rx 3 Examples of the alkyl group of are preferably those 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, and a t-butyl group.

[0231] Rx 1 ~Rx 3 Examples of the cycloalkyl group of are preferably monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.

[0232] Rx 1 ~Rx 3 Examples of the cycloalkyl group formed by the bonding of two of are preferably monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferred.

[0233] Rx 1 ~Rx 3 In the cycloalkyl group formed by the bonding of two of, for example, one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group.

[0234] The repeating unit represented by the general formula (AI) is, for example, Rx 1is a methyl group or an ethyl group, and Rx 2 and Rx 3 are preferably bonded to form the above-mentioned cycloalkyl group.

[0235] Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms), etc., and those having 8 or less carbon atoms are preferred.

[0236] As the repeating unit represented by the general formula (AI), preferably, it is an acid-decomposable (meth)acrylic acid tertiary alkyl ester-based repeating unit (Xa 1 represents a hydrogen atom or a methyl group, and T represents a single bond). More preferably, Rx 1 ~Rx 3 are each independently a repeating unit representing a linear or branched alkyl group, and still more preferably, Rx 1 ~Rx 3 are each independently a repeating unit representing a linear alkyl group.

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

[0238] In the specific examples, Rx and Xa 1 represent a hydrogen atom, CH 3 , CF 3 , or CH 2 OH. Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when there are a plurality of them, they are each 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, a cycloalkyl group having a hydroxyl group, a cyano group, an amino group, an alkylamide group, or a sulfonamide group, and preferably, it is an alkyl group having a hydroxyl group. As the branched alkyl group, an isopropyl group is particularly preferred.

[0239]

Chem.

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

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

[0242] As the lactone group, any group can be used as long as it contains a lactone structure, but preferably it is a group containing a 5- to 7-membered lactone structure, and those in which another ring structure is fused in a form that forms a bicyclo structure or a spiro structure with the 5- to 7-membered lactone structure are preferred.

[0243] It is more preferable to have a repeating unit having a group having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-16). Also, the group having 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]

Chem.

[0245] The lactone structure moiety may or may not have a substituent (Rb 2 ). Preferred substituents (Rb 2Examples thereof 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, an acid-decomposable group, etc. n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of Rb 2 may be the same or different, and a plurality of Rb 2 may combine with each other to form a ring.

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

[0247] [Chemical formula]

[0248] In general formula (AII), Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Rb 0 Preferred substituents that the alkyl group of may have include a hydroxyl group and a halogen atom. Rb 0 Examples of the halogen atom of include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb 0 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. Preferably, it is a single bond, -Ab 1 -CO 2 -represented linking group. Ab 1 is a linear or branched alkylene group, a monocyclic or polycyclic cycloalkylene group, and 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] The repeating unit having a group with a lactone structure usually has optical isomers, and any optical isomer may be used. Also, one kind of optical isomer may be used alone, or a plurality of optical isomers may be used as a mixture. When mainly using one kind of optical isomer, the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.

[0250] Specific examples of the repeating unit having a group with a lactone structure are given below, but the present invention is not limited thereto.

[0251]

Chemical formula

[0252]

Chemical formula

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

[0254] The resin (A) can further have a repeating unit containing an organic group having a polar group, particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. Thereby, the substrate adhesion and the developer affinity are improved. As the alicyclic hydrocarbon structure of the alicyclic hydrocarbon structure substituted with a polar group, an adamantyl group, a diamantyl group, and a norbornane group are preferable. As the polar group, a hydroxyl group and a cyano group are preferable.

[0255] Specific examples of the repeating unit having a polar group are given below, but the present invention is not limited thereto.

[0256] [Chemical]

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

[0258] Furthermore, as the repeating unit other than the above, a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (photoacid generator group) can also be included. In this case, the repeating unit having this photoacid generator group can be considered to correspond to the compound (B) that generates an acid upon irradiation with actinic rays or radiation described later. Examples of such a repeating unit include, for example, a repeating unit represented by the following general formula (4).

[0259] [Chemical]

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

[0261] [Chemical]

[0262] In addition, examples of the repeating unit represented by the general formula (4) include, for example, the repeating units described in paragraphs

[0094] to

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

[0263] When the resin (A) contains a repeating unit having a photoacid generator group, the content of the repeating unit having a photoacid generator group is preferably 1 to 40 mol%, more preferably 5 to 35 mol%, still more preferably 5 to 30 mol% based on all the repeating units in the resin (A).

[0264] The resin (A) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, there are a bulk polymerization method in which monomer species and an initiator are dissolved in a solvent and polymerized by heating, and a dropwise polymerization method in which a solution of monomer species and an initiator is added dropwise to a heated solvent over 1 to 10 hours. The dropwise polymerization method is preferred.

[0265] Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate; amide solvents such as dimethylformamide and dimethylacetamide; solvents that dissolve a photosensitive ray-sensitive or radiation-sensitive composition such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone described below; and the like. More preferably, polymerization is carried out using the same solvent as that used in the photosensitive ray-sensitive or radiation-sensitive composition. This can suppress the generation of particles during storage.

[0266] The polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. As the polymerization initiator, a commercially available radical initiator (such as an azo initiator or a peroxide) is used to initiate the polymerization. An azo initiator is preferred as the radical initiator, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferred. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis(2-methylpropionate), and the like. If desired, the initiator is added additionally or in portions, and after the reaction is completed, it is put into a solvent and the desired polymer is recovered by methods such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass.

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

[0268] Purification can be carried out by ordinary methods such as liquid-liquid extraction to remove residual monomers and oligomer components by combining water washing and appropriate solvents, purification methods in solution state such as ultrafiltration to extract and remove only those with a specific molecular weight or less, reprecipitation to remove residual monomers etc. by dropping a resin solution into a poor solvent to solidify the resin in the poor solvent, and purification methods in solid state such as washing the filtered resin slurry with a poor solvent.

[0269] The weight-average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and most preferably 5,000 to 15,000 in terms of polystyrene conversion value by the GPC method. By setting the weight-average molecular weight to 1,000 to 200,000, it is possible to prevent deterioration of heat resistance and dry etching resistance, and to prevent deterioration of developability and increase in viscosity resulting in deterioration of film-forming properties.

[0270] Another particularly preferred form of the weight average molecular weight of resin (A) is 3,000 to 9,500 in terms of polystyrene conversion value by the GPC method. By setting the weight average molecular weight to 3,000 to 9,500, particularly resist residues (hereinafter also referred to as "scum") are suppressed, and a better pattern can be formed.

[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 in the range of 1.2 to 2.0. The smaller the dispersity, the better the resolution, resist shape, and the smoother the side wall of the resist pattern, and the better the roughness property.

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

[0273] In addition, in the photoactive or radiation-sensitive composition, resin (A) may be used alone or in combination of a plurality of kinds.

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

[0275]

Chemical formula

[0276] In general formula (VI), R 61 、R 62 and R 63 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R 62 may be bonded to Ar 6 to form a ring, and in that case, R 62 represents a single bond or an alkylene group. X 6 represents a single bond, -COO-, or -CONR 64 -. R64 represents a hydrogen atom or an alkyl group. L 6 represents a single bond or an alkylene group. Ar 6 represents an (n + 1)-valent aromatic ring group, and when combined with R 62 to form a ring, it represents an (n + 2)-valent aromatic ring group. Y 2 When n ≥ 2, each independently represents a hydrogen atom or a group that can be eliminated by the action of an acid. However, at least one of Y 2 represents a group that can be eliminated by the action of an acid. n represents an integer from 1 to 4.

[0277] As the group Y that can be eliminated by the action of an acid 2 a structure represented by the following general formula (VI-A) is more preferable.

[0278]

Chemical formula

[0279] Here, L 1 and L 2 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group 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 that may contain a heteroatom, an aryl group that may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, or an aldehyde group. Q, M, L 1 At least two of them may combine to form a ring (preferably a 5-membered 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]

Chemical formula

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

[0283] R 3 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. M 3 represents a single bond or a divalent linking group. Q 3 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. Q 3 、M 3 and R 3 may be combined with at least two of them to form a ring. Ar 3 The aromatic ring group represented by is the same as Ar in the general formula (VI) when n in the general formula (VI) is 1, more preferably a phenylene group or a naphthylene group, and still more preferably a phenylene group. 6

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

[0285]

Chemical formula

[0286]

Chemical formula

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

[0288]

Chemical formula

[0289] In general formula (4), R 41 , R 42 and R 43 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R 42 may be bonded to L 4 to form a ring, and in that case, R 42 represents an alkylene group.

[0290] L 4 represents a single bond or a divalent linking group, and when forming a ring with R 42 represents a trivalent linking group. R 44 and R 45 represent 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. M 4 represents a single bond or a divalent linking group. Q 4 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. Q 4 , M 4 and R 44 may be bonded to each other to form a ring. R 41 , R 42 and R 43 are synonymous with R 51 , R 52 , R 53 in general formula (V) above, and the preferred ranges are also the same. L 4 is synonymous with L 5 in general formula (V) above, and the preferred ranges are also the same.

[0291] R 44 and R 45 are synonymous with R 3 in general formula (3) above, and the preferred ranges are also the same. M 4 is synonymous with M 3is synonymous and has the same preferred range. Q 4 is Q in the general formula (3) described above 3 is synonymous and has the same preferred range. Q 4 , M 4 and R 44 Examples of the ring formed by the combination of at least two of Q 3 , M 3 and R 3 include the ring formed by the combination of at least two of them, and the same applies to the preferred range.

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

[0293]

Chemical formula

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

[0295]

Chemical formula

[0296] In the general formula (BZ), AR represents an aryl group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and AR may be bonded to each other to form a non-aromatic ring.

[0297] R 1 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 the general formula (BZ) are shown below, but the present invention is not limited thereto.

[0298]

Chemical formula

[0299] [Chemical formula]

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

[0301] The content of the repeating unit having the acid-decomposable group in the resin (A) (when a plurality of types are contained, the total thereof) is preferably 5 mol% or more and 80 mol% or less, more preferably 5 mol% or more and 75 mol% or less, and still more preferably 10 mol% or more and 65 mol% or less with respect to all the repeating units in the resin (A).

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

[0303] [Chemical formula]

[0304] In the formula, R 6 and R 7 each independently represents 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 having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group. n 3 represents an integer of 0 to 6. n 4 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 the general formula (V) or the general formula (VI) are shown below, but are not limited thereto.

[0306] [Chemical formula]

[0307] The resin (A) may further have a repeating unit having a silicon atom in the side chain. Examples of the repeating unit having a silicon atom in the side chain include a (meth)acrylate-based repeating unit having a silicon atom and a vinyl-based repeating unit 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 a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, a tricyclohexylsilyl group, a tris(trimethylsiloxy)silyl group, a tris(trimethylsilyl)silyl group, a methylbis(trimethylsilyl)silyl group, a methylbis(trimethylsiloxy)silyl group, a dimethyl(trimethylsilyl)silyl group, a dimethyl(trimethylsiloxy)silyl group, or a cyclic or linear polysiloxane as described below, or a cage-type or ladder-type or random-type silsesquioxane structure. In the formula, R and R1 each independently represent a monovalent substituent. * represents a bond.

[0308] [Chemical formula]

[0309] Examples of the repeating unit having the above group preferably 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. Thereby, 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, a film thickness / line width of 3 or more), very excellent collapse performance can be exhibited.

[0311] Examples of the silsesquioxane structure include a cage-type silsesquioxane structure, a ladder-type silsesquioxane structure (a ladder-shaped silsesquioxane structure), a random-type silsesquioxane structure, and the like. Among them, the cage-type silsesquioxane structure is preferred.

[0312] Here, the cage-type silsesquioxane structure is a silsesquioxane structure having a cage-like skeleton. The cage-type silsesquioxane structure may be a complete cage-type silsesquioxane structure or an incomplete cage-type silsesquioxane structure, but a complete cage-type silsesquioxane structure is preferred.

[0313] The ladder-type silsesquioxane structure is a silsesquioxane structure having a ladder-shaped skeleton. The random-type silsesquioxane structure is a silsesquioxane structure with a random skeleton.

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

[0315]

Chemical formula

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

[0317] The organic group is not particularly limited. 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 imide group, a phosphino group, a phosphinyl group, a silyl group, a vinyl group, a hydrocarbon group which may have a hetero atom, a (meth)acrylic group-containing group, and an epoxy group-containing group.

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

[0319] Examples of the hydrocarbon group of the hydrocarbon group which may have the above heteroatom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group combining these.

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

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

[0322] When the resin (A) has a repeating unit having a silicon atom in the above side chain, its content is preferably 1 to 30 mol%, more preferably 5 to 25 mol%, and even more preferably 5 to 20 mol% based on all the repeating units in the resin (A).

[0323] (B) A compound that generates an acid upon exposure to actinic rays or radiation (photoacid generator) The radiation-sensitive or actinic ray-sensitive resin composition preferably contains a compound that generates an acid upon exposure to actinic rays or radiation (hereinafter also referred to as "photoacid generator 《PAG:Photo Acid Generator》").

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

[0325] When the photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.

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

[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 one, but a compound that generates at least one of an organic acid, such as sulfonic acid, bis(alkylsulfonyl)imide, or tris(alkylsulfonyl)methide, upon irradiation with actinic rays or radiation, preferably electron beams or extreme ultraviolet rays, is preferred.

[0329] More preferably, compounds represented by the following general formulas (ZI), (ZII), and (ZIII) can be mentioned.

[0330]

Chemical formula

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

[0332] Also, two of R 201 ~R 203 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. R 201 ~R 203Examples of the group formed by combining two of them include alkylene groups (e.g., butylene group, pentylene group).

[0333] Z - represents a non-nucleophilic anion (an anion with extremely low ability to cause nucleophilic reaction).

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

[0335] The aliphatic moiety in aliphatic sulfonate anions and aliphatic carboxylate anions may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms.

[0336] Examples of the aromatic group in aromatic sulfonate anions and aromatic carboxylate anions preferably include aryl groups having 6 to 14 carbon atoms, such as phenyl group, tolyl group, naphthyl group, etc.

[0337] The alkyl group, cycloalkyl group, and aryl group mentioned above may have substituents. Specific examples of such substituents include a nitro group, halogen atoms 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), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like.

[0338] Regarding the aryl group and ring structure of each group, an alkyl group (preferably having 1 to 15 carbon atoms) can be further mentioned as a substituent.

[0339] As the aralkyl group in the aralkylcarboxylic acid anion, an aralkyl group having preferably 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylbutyl group, etc., can be mentioned.

[0340] As the sulfonylimide anion, for example, a saccharin anion can be mentioned.

[0341] In the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion, the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the substituents of 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, a cycloalkylaryloxysulfonyl group, etc., and a fluorine atom or an alkyl group substituted with a fluorine atom is preferable.

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

[0343] Examples of other non-nucleophilic anions include fluorinated phosphorus (e.g., PF 6 - ), fluorinated boron (e.g., BF 4 - ), fluorinated antimony (e.g., SbF 6 - ), etc.

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

[0345] From the viewpoint of acid strength, it is preferable that the pKa of the generated acid is -1 or less for improving the sensitivity.

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

[0347]

Chemical formula

[0348] In the formula, Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group, and when there are a plurality of R 1 and R 2 they may be the same or different from each other. L represents a divalent linking group, and when there are a plurality of Ls, they may be the same or different from each other. A represents a cyclic organic group. x represents an integer from 1 to 20, y represents an integer from 0 to 10, and z represents an integer from 0 to 10.

[0349] The general formula (AN1) will be described 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. Further, the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.

[0350] Preferably, Xf is a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include a fluorine atom, CF 3 、C 2 F 5 、C 3 F 7 、C 4 F 9 、CH 2 CF 3 、CH 2 CH 2 CF 3 、CH 2C 2 F 5 、 CH 2 CH 2 C 2 F 5 、 CH 2 C 3 F 7 、 CH 2 CH 2 C 3 F 7 、 CH 2 C 4 F 9 、 CH 2 CH 2 C 4 F 9 include, among others, fluorine atoms, CF 3 is preferred. Particularly, it is preferred that both Xf are fluorine atoms.

[0351] R 1 、 R 2 's alkyl group may have a substituent (preferably a fluorine atom), and those having 1 to 4 carbon atoms are preferred. More preferably, it is a perfluoroalkyl group having 1 to 4 carbon atoms. R 1 、 R 2 Specific examples of the alkyl group having a substituent include CF 3 、 C 2 F 5 、 C 3 F 7 、 C 4 F 9 、 C 5 F 11 、 C 6 F 13 、 C 7 F 15 、 C 8 F 17 、 CH 2 CF 3 、 CH 2 CH 2 CF 3 、 CH 2 C 2 F 5 、 CH 2 CH 2 C 2 F 5 、 CH 2 C 3 F7 、 CH 2 CH 2 C 3 F 7 、 CH 2 C 4 F 9 、 CH 2 CH 2 C 4 F 9 are exemplified, and among them, CF 3 is preferred.

[0352] R 1 、 R 2 As, preferably, a fluorine atom or CF 3 is. x is preferably from 1 to 10, more preferably from 1 to 5. y is preferably from 0 to 4, more preferably 0. z is preferably from 0 to 5, more preferably from 0 to 3.

[0353] The divalent linking group of L is not particularly limited, and examples thereof include ―COO-, -OCO-, -CO-, -O-, -S―, -SO―, ―SO 2 -, an alkylene group, a cycloalkylene group, an alkenylene group, or a linking group formed by linking a plurality of these, and a linking group having 12 or less carbon atoms in total is preferred. Among these, ―COO-, -OCO-, -CO-, -O- are preferred, and ―COO-, -OCO- are more preferred.

[0354] In the above general formula (ANI), as a combination of partial structures other than A, SO 3- -CF 2 -CH 2 -OCO-, SO 3- -CF 2 -CHF-CH 2 -OCO-, SO 3- -CF 2 -COO-, SO 3- -CF 2 -CF 2 -CH 2 -, SO 3- -CF 2 -CH(CF 3 )-OCO- can be mentioned as preferred ones.

[0355] As the cyclic organic group of A, there is no particular limitation 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 not having aromaticity).

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

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

[0358] Examples of the heterocyclic group include those derived from furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring. Among them, those derived from furan ring, thiophene ring, and pyridine ring are preferable.

[0359] In addition, as the cyclic organic group, a lactone structure can also be mentioned, and specific examples include lactone structures represented by the following general formulas (LC1-1) to (LC1-17).

[0360]

Chemical formula

[0361] The above-mentioned cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear, branched, or cyclic, preferably having 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic, polycyclic, or spirocyclic, preferably having 3 to 20 carbon atoms), an aryl group (preferably having 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 sulfonic acid ester group, etc. Note that the carbon atoms (carbons contributing to ring formation) constituting the cyclic organic group may be carbonyl carbons.

[0362] Note that the above-mentioned substituent corresponds to Rb in the above (LC1-1) to (LC1-17). 2 In the above (LC1-1) to (LC1-17), n2 represents an integer from 0 to 4. When n2 is 2 or more, a plurality of Rb 2 may be the same or different, and a plurality of Rb 2 may combine with each other to form a ring.

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

[0364] Of R 201 , R 202 and R 203 , at least one is preferably an aryl group, and more preferably all three are aryl groups. Examples of the aryl group include, in addition to a phenyl group and a naphthyl group, heteroaryl groups such as an indole residue and a pyrrole residue. R 201 to R 203Examples of the alkyl group and cycloalkyl group include preferably linear or branched alkyl groups having 1 to 10 carbon atoms and cycloalkyl groups having 3 to 10 carbon atoms. More preferably, examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, etc. More preferably, examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, etc. 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), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), etc., but are not limited thereto.

[0365] Next, the general formulas (ZII) and (ZIII) will be described. In the 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 groups of R 204 ~R 207 are preferably a phenyl group and a naphthyl group, and more preferably a phenyl group. The aryl groups of R

[0367] R 204 ~R 207Examples of the alkyl group and cycloalkyl group include preferably linear or branched alkyl groups having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group).

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

[0369] In the general formula (ZII), Z - represents a non-nucleophilic anion. Specifically, it is the same as that described for Z - in the general formula (ZI), and the preferred forms are also the same.

[0370] Hereinafter, specific examples of the general formulas (ZI) to (ZIII) are shown, but the invention is not limited thereto.

[0371]

Chemical formula

[0372] In the present invention, from the viewpoint of suppressing the diffusion of the acid generated by exposure to the unexposed portion and improving the resolution, the above photoacid generator may be a compound that generates an acid having a size of 130 Å 3 or more in volume (more preferably sulfonic acid), and more preferably a compound that generates an acid having a size of 190 Å 3 or more in volume (more preferably sulfonic acid), and an acid having a size of 270 Å 3It is more preferable that the compound generates an acid (more preferably sulfonic acid) having the above size, with a volume of 400 Å 3 Particularly preferably, the compound generates an acid (more preferably sulfonic acid) having the above size. However, from the viewpoints of sensitivity and coating solvent solubility, the above volume is preferably 2000 Å 3 or less, and more preferably 1500 Å 3 or less. The value of the above volume was determined using "WinMOPAC" manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid according to each example is input, and then, using the molecular force field calculation using the MM3 method with this structure as the initial structure, the most stable conformation of each acid is determined. After that, the "accessible volume" of each acid can be calculated by performing molecular orbital calculations using the PM3 method on these most stable conformations.

[0373] In the present invention, a photoacid generator that generates an acid exemplified below upon irradiation with actinic rays or radiation is preferable. In some of the examples, the calculated value of the volume is appended (unit Å 3 ). The calculated value obtained here is the volume value of the acid in which a proton is bonded to the anion part.

[0374]

Chemical formula

[0375]

Chemical formula

[0376]

Chemical formula

[0377] As the photoacid generator, paragraphs

[0368] to

[0377] of JP-A-2014-41328 and paragraphs

[0240] to

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

[0339] of the corresponding U.S. Patent Application Publication No. 2015 / 004533) can be incorporated herein by reference, and the contents thereof are incorporated into this specification. Further, the following compounds are given as preferred specific examples, but are not limited thereto.

[0378] [Chemical formula]

[0379] [Chemical formula]

[0380] [Chemical formula]

[0381] [Chemical formula]

[0382] The photoacid generator can be used alone or in combination of two or more.

[0383] The content of the photoacid generator in the photosensitive or radiation-sensitive resin composition is preferably 0.1 to 50% by mass, more preferably 5 to 50% by mass, still more preferably 8 to 40% by mass, based on the total solid content of the composition. In particular, for achieving both high sensitivity and high resolution during electron beam or extreme ultraviolet exposure, a higher content of the photoacid generator is preferably, more preferably 10 to 40% by mass, and most preferably 10 to 35% by mass.

[0384] (C) Solvent When preparing a photosensitive or radiation-sensitive resin composition by dissolving each of the above-described components, a solvent can be used. Examples of solvents 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] Examples of alkylene glycol monoalkyl ether carboxylates include preferably 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] Examples of alkylene glycol monoalkyl ethers include preferably 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] Examples of alkyl lactates include preferably methyl lactate, ethyl lactate, propyl lactate, and butyl lactate.

[0388] Examples of alkyl alkoxypropionates include preferably ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.

[0389] Examples of cyclic lactones having 4 to 10 carbon atoms include, for example, 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 optionally containing a ring include, for example, 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-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] Examples of alkylene carbonates include, for example, propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.

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

[0393] Examples of the alkyl pyruvate include preferably methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

[0394] Preferred solvents that can be used include solvents having a boiling point of 130°C or higher under normal temperature and pressure. Specifically, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate, and propylene carbonate can be mentioned. In the present invention, the above solvents may be used alone or in combination of two or more.

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

[0396] Examples of the solvent containing a hydroxyl group include, for example, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, etc. Among these, propylene glycol monomethyl ether and ethyl lactate are particularly preferred.

[0397] Examples of the solvent that does not contain a hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, etc. Among 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 and the solvent not containing a hydroxyl group is preferably 1 / 99 to 99 / 1, more preferably 10 / 90 to 90 / 10, and still more preferably 20 / 80 to 60 / 40. A mixed solvent containing 50% by mass or more of the 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 kinds containing propylene glycol monomethyl ether acetate. As the solvent, for example, the solvents described in paragraphs 0013 to 0029 of JP-A-2014-219664 can also be used.

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

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

[0402]

Chemical formula

[0403] In the general formulas (A) and (E), R 200 , R201 and R 202 may be the same or different and each represents 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] Regarding the above alkyl group, as the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferable. R 203 、R 204 、R 205 and R 206 may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms. The alkyl groups in these general formulas (A) and (E) are more preferably unsubstituted.

[0405] Preferable compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, etc. More preferable 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, aniline derivatives having a hydroxyl group and / or an ether bond, etc.

[0406] Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and the like. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]nona-5-ene, 1,8-diazabicyclo[5,4,0]undeca-7-ene, and the like. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, and the like. Examples of the compound having an onium carboxylate structure are those in which the anion part of the compound having an onium hydroxide structure becomes carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, perfluoroalkylcarboxylate, and the like. Examples of the compound having a trialkylamine structure include tri(n-butyl)amine, tri(n-octyl)amine, and the like. Examples of the aniline compound include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, N,N-dihexylaniline, and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, tris(methoxyethoxyethyl)amine, and the like. Examples of the aniline derivative having a hydroxyl group and / or an ether bond include N,N-bis(hydroxyethyl)aniline, and the like.

[0407] Preferred basic compounds further include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group.

[0408] As the amine compound, primary, secondary, and tertiary amine compounds can be used, and an amine compound in which at least one alkyl group is bonded to the nitrogen atom is preferred. The amine compound is more preferably a tertiary amine compound. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to the nitrogen atom in the amine compound, in addition to the alkyl group, a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 12 carbon atoms) may be bonded to the nitrogen atom.

[0409] In addition, it is preferable that the amine compound has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (-CH 2 CH 2 O-) or an oxypropylene group (-CH(CH 3 )CH 2 O- or -CH 2 CH 2 CH 2 O-) is preferred, and more preferably an oxyethylene group.

[0410] As the ammonium salt compound, primary, secondary, tertiary, and quaternary ammonium salt compounds can be used, and an ammonium salt compound in which at least one alkyl group is bonded to the nitrogen atom is preferred. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to the nitrogen atom in the ammonium salt compound, in addition to the alkyl group, a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 12 carbon atoms) may be bonded to the nitrogen atom.

[0411] It is preferable that the ammonium salt compound has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (-CH 2 CH 2 O-) or an oxypropylene group (-CH(CH3 ) CH 2 O - or - CH 2 CH 2 CH 2 O - ) is preferred, and more preferably an oxyethylene group.

[0412] Examples of the anion of the ammonium salt compound include a halogen atom, sulfonate, borate, phosphate, etc. Among them, a halogen atom and sulfonate are preferred. As the halogen atom, chloride, bromide, and iodide are particularly preferred. As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferred. Examples of the organic sulfonate include an alkyl sulfonate and an aryl sulfonate 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, an aryl group, etc. Specific examples of the alkyl sulfonate include methanesulfonate, ethanesulfonate, butanesulfonate, hexanesulfonate, octanesulfonate, benzylsulfonate, trifluoromethanesulfonate, pentafluoroethanesulfonate, nonafluorobutanesulfonate, etc. 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 as the substituent, a linear or branched alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms are preferred. Specific examples of the linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n - propyl, isopropyl, n - butyl, i - butyl, t - butyl, n - hexyl, cyclohexyl, etc. Other substituents include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, an acyloxy group, etc.

[0413] An amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal on the side 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, an aryloxy group, etc. The substitution position of the substituent may be any of the 2nd to 6th positions. The number of substituents may be any in the range of 1 to 5.

[0414] It is preferable to have at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (-CH 2 CH 2 O-) or an oxypropylene group (-CH(CH 3 )CH 2 O- or -CH 2 CH 2 CH 2 O-) is preferable, and more preferably an oxyethylene group.

[0415] The amine compound having a phenoxy group can be obtained by heating and reacting a primary or secondary amine having a phenoxy group with a haloalkyl ether, adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, tetraalkylammonium, etc., and then extracting with an organic solvent such as ethyl acetate, chloroform, etc. Alternatively, it can be obtained by heating and reacting a primary or secondary amine with a haloalkyl ether having a phenoxy group at the terminal, adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, tetraalkylammonium, etc., and then extracting with an organic solvent such as ethyl acetate, chloroform, etc. (A compound (PA) having a proton acceptor functional group and generating a compound whose proton acceptor property decreases, disappears, or changes from a proton acceptor property to an acidic property upon irradiation with actinic rays or radiation) The composition according to the present invention may further contain, as a basic compound, a compound having a proton acceptor functional group and generating a compound whose proton acceptor property decreases, disappears, or changes from a proton acceptor property to an acidic property upon irradiation with actinic rays or radiation [hereinafter also referred to as compound (PA)].

[0416] The proton acceptor functional group is a group that can interact electrostatically with a proton or a functional group having electrons, and means, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group having a nitrogen atom having an unshared electron pair that does not contribute to π-conjugation. The nitrogen atom having an unshared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula.

[0417] [Chemical formula]

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

[0419] Compound (PA) generates a compound whose proton acceptor property decreases, disappears, or changes from a proton acceptor property to an acidic property upon irradiation with actinic rays or radiation. Here, the decrease, disappearance, or change from a proton acceptor property to an acidic property of the proton acceptor property is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group. Specifically, when a proton adduct is formed from a compound (PA) having a proton acceptor functional group and a proton, it means that the equilibrium constant in the chemical equilibrium decreases.

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

[0421]

Chemical formula

[0422]

Chemical formula

[0423]

Chemical formula

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

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

[0426] The use ratio of the photoacid generator and the basic compound in the composition is preferably such that photoacid generator / basic compound (molar ratio) = 2.5 to 300. That is, from the viewpoints of sensitivity and resolution, a molar ratio of 2.5 or more is preferable, and from the viewpoint of suppressing a decrease in resolution due to thickening of the resist pattern over time until post-exposure heat treatment, 300 or less is preferable. The photoacid generator / basic compound (molar ratio) is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

[0427] As the basic compound, for example, the compounds (amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc.) described in paragraphs 0140 to 0144 of JP-A-2013-11833 can be used.

[0428] (A’) Hydrophobic resin The radiation-sensitive or actinic ray-sensitive resin composition may have a hydrophobic resin (A’) separately from the above resin (A).

[0429] The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film. However, unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule and does not necessarily have to contribute to uniformly mixing polar / non-polar substances. As the effect of adding the hydrophobic resin, control of the static / dynamic contact angle of the resist film surface with respect to water, suppression of outgassing, etc. can be cited.

[0430] From the viewpoint of uneven distribution on the film surface layer, the hydrophobic resin preferably has any one or more of "fluorine atom", "silicon atom", and "CH partial structure contained in the side chain portion of the resin", and more preferably has two or more. Further, the above hydrophobic resin preferably contains a hydrocarbon group having 5 or more carbon atoms. These groups may be in the main chain of the resin or may be substituted in the side chain. 3 When the hydrophobic resin contains a fluorine atom and / or a silicon atom, the above fluorine atom and / or silicon atom in the hydrophobic resin may be contained in the main chain of the resin or may be contained in the side chain.

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

[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 is substituted with a fluorine atom, and may further have a substituent other than the fluorine atom.

[0433] The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than the fluorine atom.

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

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

[0436] Also, as described above, it is also preferable that the hydrophobic resin contains a CH 3 partial structure in the side chain portion. Here, the CH 3 partial structure possessed by the side chain portion in the hydrophobic resin includes the CH 3 partial structure possessed by an ethyl group, a propyl group, etc.

[0437] On the other hand, the methyl group directly bonded to the main chain of the hydrophobic resin (for example, the α-methyl group of the repeating unit having a methacrylic acid structure) has little contribution to the surface segregation of the hydrophobic resin due to the influence of the main chain. Therefore, it is not included in the CH 3 partial structure in the present invention.

[0438] Regarding the hydrophobic resin, the descriptions in

[0348] to

[0415] of JP-A-2014-010245 can be referred to, and these contents are incorporated herein. In addition, as the hydrophobic resin, those described in JP-A-2011-248019, JP-A-2010-175859, and JP-A-2012-032544 can also be preferably used.

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

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

[0441] Examples of the fluorine-based and / or silicon-based surfactant include the surfactants described in

[0276] of US Patent Application Publication No. 2008 / 0248425. Also, F-Top EF301 or EF303 (manufactured by Shin-Akita Chemical 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.); Troyzol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toagosei 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 Gemco Co., Ltd.); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA Solutions Inc.); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos Co., Ltd.) may be used. In addition, the polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

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

[0443] Also, surfactants other than fluorine-based and / or silicon-based surfactants described in

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

[0444] When the radiation-sensitive or radiation-sensitive resin composition contains a surfactant, its content is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, still more preferably 0.0005 to 1% by mass based on the total solid content of the composition.

[0445] (F) Other Additives The radiation-sensitive or radiation-sensitive resin composition may further contain a dissolution inhibitor 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 1000 or less, or an alicyclic or aliphatic compound containing a carboxy group).

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

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

[0448] [Upper Layer Film (Top Coat Film)] In the pattern forming method of the present invention, an upper layer film (top coat 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 uniformly applied on the upper layer of 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, the upper layer film can be formed based on the description in paragraphs 0072 to 0082 of JP-A-2014-059543. In addition to the polymer described in paragraph 0072 of JP-A-2014-059543, a hydrophobic resin or the like can also be used as the material for forming the upper layer film. As the hydrophobic resin, for example, the above-described hydrophobic resin (A') can be used.

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

[0452] Further, it is preferable that the upper layer film 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 ones as the photoacid generators that can be contained in a photoactive ray-sensitive or radiation-sensitive composition (for example, the above-described photoacid generator (B)) can be used.

[0454] Hereinafter, the resins preferably used for the upper layer film (top coat film) will be described.

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

[0456] Regarding the hydrophobic resin, the descriptions in

[0017] to

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

[0017] to

[0023] of US Patent Publication No. 2013 / 244438) and

[0016] to

[0165] of JP-A-2014-56194 can be referred to, and these contents are incorporated herein.

[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, particularly in the case of electron beam or EUV exposure, the generation efficiency of secondary electrons and the acid generation efficiency from a compound that generates an acid by actinic rays or radiation are increased, and effects of high sensitivity and high resolution can be expected during pattern formation. The weight average molecular weight of the resin is preferably from 3,000 to 100,000, more preferably from 3,000 to 30,000, and most preferably from 5,000 to 20,000. The blending amount of the resin in the composition for forming the upper layer film is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, still more preferably 70 to 99.7% by mass, and even more preferably 80 to 99.5% by mass in the total solid content.

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

[0459] The preferable range of the content of the fluorine atom and the silicon atom contained in the resin (XA) is that the repeating unit containing a fluorine atom and / or a silicon atom is preferably 10 to 100% by mass, preferably 10 to 99 mol%, and more preferably 20 to 80 mol% in the resin (XA).

[0460] Furthermore, it is more preferable that the composition for forming the upper layer film contains at least one resin (XA) having a fluorine atom and / or a silicon atom, and a resin (XB) having a content of fluorine atom and / or silicon atom smaller than that of the resin (XA). Thereby, when the upper layer film is formed, the resin (XA) is unevenly distributed on the surface of the upper layer film, so that the performance such as development characteristics and immersion liquid followability can be improved.

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

[0462] As the resin (XB), a form that does not substantially contain a fluorine atom and a silicon atom is preferable. In this case, specifically, the total content of the repeating unit having a fluorine atom and the repeating unit having a silicon atom 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%, that is, does not contain a fluorine atom and a silicon atom, with respect to all the repeating units in the resin (XB).

[0463] <Method for preparing the composition for forming the upper layer film (top coat composition)> The composition for forming the upper layer film is preferably prepared by dissolving each component in a solvent and filtering it through a filter. As the filter, those 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 are preferred. Note that a plurality of types of filters may be connected in series or in parallel for use. Also, the composition may be filtered multiple times, and the process of filtering multiple times may be a circulation filtration process. Furthermore, degassing treatment or the like may be performed on the composition before and after filter filtration. The composition for forming the upper layer film preferably does not contain impurities such as metals. The content of the 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 particularly preferably substantially not contained (being below the detection limit of the measuring device).

[0464] In the above-mentioned <exposure step>, when the exposure is liquid immersion exposure, the upper layer film is disposed between the photosensitive or radiation-sensitive film and the immersion liquid, and also functions as a layer that does not directly contact the photosensitive or radiation-sensitive film with the immersion liquid. In this case, the preferable characteristics that the upper layer film (composition for forming the upper layer film) should have are coating suitability for the photosensitive or radiation-sensitive film, transparency to radiation, particularly 193 nm, and low solubility in the immersion liquid (preferably water). Also, it is preferable that the upper layer film does not mix with the photosensitive or radiation-sensitive film and can be uniformly coated on the surface of the photosensitive or radiation-sensitive film.

[0465] In order to uniformly coat the composition for forming the upper layer film on the surface of the photosensitive or radiation-sensitive film without dissolving the photosensitive or radiation-sensitive film, the composition for forming the upper layer film preferably contains a solvent that does not dissolve the photosensitive or radiation-sensitive film. As the solvent that does not dissolve the photosensitive or radiation-sensitive film, it is more preferable to use a solvent having components different from the developer containing an organic solvent (organic-based developer).

[0466] The coating method of the composition for forming the upper layer film is not particularly limited, and conventionally known spin coating method, spray method, roller coating method, dipping method, etc. can be used.

[0467] The film 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 with a thickness of 5 nm to 300 nm, preferably 10 nm to 300 nm, more preferably 20 nm to 200 nm, and still more preferably 30 nm to 100 nm.

[0468] After forming the upper layer film, 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 photosensitive radiation-sensitive film. The upper layer film is preferably insoluble in the immersion liquid, and more preferably insoluble in water. From the viewpoint of immersion liquid followability, the receding contact angle of the immersion liquid with respect to the upper layer film is preferably 50 to 100 degrees, and more preferably 80 to 100 degrees (23 °C).

[0469] In immersion exposure, since the immersion liquid needs to move on the wafer following the movement of the exposure head scanning at high speed on the wafer to form an exposure pattern, the contact angle of the immersion liquid with respect to the photosensitive radiation-sensitive film in a dynamic state becomes important. In order to obtain better resist performance, it is preferable to have a receding contact angle within the above range.

[0470] When peeling the upper layer film, an organic developer may be used, or a separate peeling liquid may be used. As the peeling liquid, a solvent with little penetration into the photosensitive radiation-sensitive film is preferable. In terms of being able to peel the upper layer film simultaneously with the development of the photosensitive radiation-sensitive film, the upper layer film is preferably peelable with an organic developer. The organic developer used for peeling is not particularly limited as long as it can dissolve and remove the low-exposure part of the photosensitive radiation-sensitive film.

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

[0472] Here, the dissolution rate of the upper layer film in the organic developer is the film thickness reduction rate when the upper layer film is exposed to the developer after film formation, and in the present invention, it is the rate when immersed in butyl acetate at 23°C.

[0473] By setting the dissolution rate of the upper layer film in the organic developer to 1 / sec or more, preferably 10 nm / sec or more, there is an effect of reducing the occurrence of development defects after developing the photosensitive or radiation-sensitive film. Also, by setting it to 300 nm / sec or less, preferably 100 nm / sec, presumably due to the effect of reducing exposure unevenness during immersion exposure, there is an effect that the line edge roughness of the pattern after developing the photosensitive or radiation-sensitive film becomes better.

[0474] The upper layer film may also be removed using other known developers, such as an alkaline aqueous solution. Specifically, an aqueous solution of tetramethylammonium hydroxide can be mentioned as the alkaline aqueous solution that can be used.

[0475] The present invention also relates to a method for manufacturing an electronic device, including the above-described pattern formation method of the present invention.

[0476] The electronic device manufactured by the method for manufacturing an electronic device of the present invention is preferably mounted on electric and electronic devices (such as home appliances, OA (Office Automation), media-related devices, optical devices, and communication devices, etc.).

Examples

[0477] Hereinafter, the present invention will be described in detail 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 Liquids for Semiconductor Manufacturing>> Examples of the synthesis of various processing liquids will be described below. However, the present invention is not limited to the following synthesis examples, and they can be synthesized using known methods.

[0479] [Examples 1 to 46, Comparative Examples 1 and 2] <Purification of Raw Materials and the Like> For each raw material and each catalyst used in each of the examples shown below, high-purity grades with a purity of 99% by mass or more were used, and they were further purified by distillation, ion exchange, filtration, etc. in advance. Also, 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 is also possible to supply dilute sulfuric acid and use it while dehydrating it to a predetermined concentration range.

[0480] The ultrapure water used in the examples was purified by the method described in JP-A-2007-254168, and after confirming by measurement using the SP-ICP-MS method described below that the content rates of each of the elements Na, Ca, and Fe were less than 10 mass ppt with respect to the total mass of each treatment liquid, it was used for the adjustment of the treatment liquid.

[0481] The preparation, filling, storage, and analysis measurement of the treatment liquid were all carried out in a clean room at a level that satisfies ISO class 2 or lower. Also, the containers used in the examples were used after being washed in advance with the treatment liquid of the present invention.

[0482] <Synthesis Example 1> Synthesis of Butyl Acetate-Containing Treatment Liquid (Treatment Liquid 1A) (Step 1) Acetic acid and n-butanol were pre-reacted in a continuous tank reactor in the presence of sulfuric acid as a catalyst. Next, the obtained reaction liquid 1a was reacted in a continuous reactive distillation column while removing the water by-produced as an azeotropic mixture of butyl acetate / n-butanol / water from the top of the distillation column to the outside of the system, thereby obtaining a crude liquid containing butyl acetate (hereinafter referred to as "crude butyl acetate liquid") 1b.

[0483] (Step 2) Regarding the crude butyl acetate liquid 1b obtained in Step 1, the sulfuric acid content was neutralized with an alkali. Next, after washing with water, water was removed to take out a crude butyl acetate liquid 1c.

[0484] (Step 3) The crude butyl acetate 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 crude butyl acetate liquid 1d containing butyl acetate, n-butanol, water, sulfuric acid, and trace amounts of by-products was fed into a distillation column for the purpose of removing low-boiling substances such as the impurity n-butanol and water. Thereafter, distillation was repeated multiple times to obtain a butyl acetate-containing treatment liquid (treatment liquid 1A), which is the target product.

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

[0486]

Chemical formula

[0487] Using the same method as in Synthesis Example 1, other butyl acetate-containing treatment liquids (treatment liquids 1B to 1Q) were synthesized. Compound (B) contained in each of the obtained treatment liquids was the same as that in treatment liquid 1A, and the content rate of each compound (B) in the treatment liquid satisfied requirement (b) (see Table 2).

[0488] <Synthesis Example 2> Synthesis of 1-hexanol-containing treatment liquid (treatment liquid 2A) (Raw materials, etc.) 1-Hexanol is synthesized according to the following two-step reaction formula.

[0489] Al(C 2 H 5 ) 3 +6C 2 H 4 →Al(C 6 H 13 ) 3 Al(C 6 H 13 ) 3 +3 / 2O 2 +3H 2 O→3HOC 6 H 13 +Al(OH) 3 (Step 1) By a known method, Al(C polymerized by the above-mentioned first-stage reaction 6 H 15 ) 3 was obtained. Subsequently, using this Al(C 6 H 15 ) 3 as a catalyst, in the coexistence of oxygen and water, the synthesis of 1-hexanol was carried out according to a known method. Therein, heat treatment was performed at 40 °C for 10 hours to obtain a crude liquid containing 1-hexanol (hereinafter referred to as "1-hexanol crude liquid") 2a. Al was removed as aluminum hydroxide.

[0490] (Step 2) Since the 1-hexanol crude liquid 2a obtained in Step 1 contains a precipitate of Al(OH) 3 , the removal of Al(OH) 3 was carried out by filtration to obtain 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-products such as substitution isomers and higher alcohols. Thereafter, distillation was repeated a plurality of times to obtain a 1-hexanol-containing treatment liquid (treatment liquid 2A) which is a target substance.

[0492] Compound (B) contained in the obtained 1-hexanol-containing treatment liquid (treatment liquid 2A) was the following compound. All of these compounds satisfied requirement (b) in terms of the content rate in the treatment liquid (see Table 2).

[0493] [Chemical formula]

[0494] [Synthesis Example 3] Synthesis of 4-methyl-2-pentanol-containing treatment liquid (treatment liquid 3A) (Step 1) cis-4-methyl-2-pentene as Ipc as a catalyst 2In the presence of BH (Diisopinocampheylborane), the synthesis of 4-methyl-2-pentanol was carried out according to a known method. Therein, heat treatment was performed at 80 °C for 4 hours, and through an intermediate in which Ipc 2 BH was bonded via boron, a crude liquid containing 4-methyl-2-pentanol (hereinafter referred to as "4-methyl-2-pentanol crude liquid") 3a was obtained.

[0495] (Step 2) The 4-methyl-2-pentanol crude 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 the purpose of purification. Distillation was repeated a plurality of times to obtain a treatment liquid containing 4-methyl-2-pentanol as the target organism (treatment liquid 3A).

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

[0497] [Chemical formula]

[0498] In the same manner as in Synthesis Example 3, other treatment liquids containing 4-methyl-2-pentanol (treatment liquids 3B to 3G) were synthesized. The compound (B) contained in each obtained treatment liquid was the same as that in treatment liquid 1A, and all of the compounds (B) satisfied the requirement (b) in terms of the content rate in the treatment liquid (see Table 2).

[0499] [Synthesis Example 4] Synthesis of a treatment liquid containing PGMEA (propylene glycol monomethyl ether acetate) (treatment liquid 4A) (Step 1) Propylene oxide, methanol, and acetic acid were used to synthesize PGMEA (two-step synthesis) according to a known method in the presence of sulfuric acid as a catalyst. Therein, heat treatment was performed at 80 °C for 8 hours to obtain a crude liquid containing PGMEA (hereinafter referred to as "PGMEA crude liquid") 4a.

[0500] (Step 2) The PGMEA crude liquid 4a obtained in Step 1 contains unreacted propylene oxide, methanol, acetic acid, and substitution isomers as impurities. For the purpose of purifying this PGMEA crude liquid 4a, it was fed into a distillation column. Distillation was repeated multiple times to obtain a treatment liquid containing PEGMEA (treatment liquid 4A) as the target organism. Compound (B) contained in the obtained treatment liquid containing PGMEA (treatment liquid 4A) was the following compound. In all of these compounds, the content rate in the treatment liquid satisfied requirement (b) (see Table 2).

[0501] [Chemical formula]

[0502] Other treatment liquids containing PGMEA (treatment liquids 4B to 4E) were synthesized in the same manner as in Synthesis Example 4. Compound (B) contained in each of the obtained treatment liquids was the same as that in treatment liquid 4A, and the content rate of each compound (B) in the treatment liquid satisfied requirement (b) (see Table 2).

[0503] [Synthesis Example 5] Synthesis of a treatment liquid containing IPA (isopropanol) (treatment liquid 5A) (Step 1) Using acetone and hydrogen, a reduction reaction of acetone was carried out according to a known method in the presence of copper oxide - zinc oxide - aluminum oxide as a catalyst. Therein, heat treatment was performed at 100 °C for 4 hours to obtain a crude liquid containing IPA (hereinafter referred to as "IPA crude liquid") 5a.

[0504] (Step 2) The IPA crude liquid 5a contains unreacted acetone, substitution isomers as impurities, and a catalyst. For the purpose of purifying this IPA crude liquid 5a, it was supplied to a distillation column. Distillation was repeated multiple times to obtain a processed liquid containing IPA (processed liquid 5A), which is the target substance.

[0505] Compound (B) contained in the obtained processed liquid containing IPA (processed liquid 5A) was the following compound. All of these compounds satisfied requirement (b) in terms of the content rate in the processed liquid (see Table 2).

[0506]

Chemical formula

[0507] Using the same method as in Synthesis Example 5, other processed liquids containing IPA (processed liquids 5B to 5E) were synthesized. Compound (B) contained in each of the obtained processed liquids was the same as that in processed liquid 5A, and all of the compounds (B) satisfied requirement (b) in terms of the content rate in the processed liquid (see Table 2).

[0508] <Synthesis Example 6> Synthesis of a processed liquid containing ethyl lactate (Ethyl lactate; EL) (processed liquid 6A) (Step 1) Using lactic acid and ethanol, a crude liquid containing ethyl lactate (hereinafter referred to as "lactic acid crude liquid") 6a was obtained by the esterification method described in JP-A-62-26249.

[0509] (Step 2) The ethyl lactate crude liquid 6a obtained in Step 1 contains by-produced water or alcohol and unreacted raw material ethanol. For the purpose of purifying the obtained ethyl lactate crude liquid 6a, it was supplied to a distillation column. Thereafter, distillation was repeated multiple times to obtain a processed liquid containing ethyl lactate (processed liquid 6A).

[0510] Compound (B) contained in the obtained processed liquid containing ethyl lactate (processed liquid 6A) was the following compound. All of these compounds satisfied requirement (b) in terms of the content rate in the processed liquid (see Table 2).

[0511]

Chem.

[0512] In the same manner as in Synthesis Example 6, other ethyl lactate-containing treatment liquids (treatment liquids 6B to 6E) were synthesized. The compound (B) contained in each of the obtained treatment liquids was the same as that in treatment liquid 6A, and the content rate of each compound (B) in the treatment liquid satisfied requirement (b) (see Table 2).

[0513] <Synthesis Example 7> Synthesis of cyclohexanone-containing treatment liquid (treatment liquid 7A) (Step 1) By the method described in JP-A-2007-63209, 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 "cyclohexanone crude liquid") 7a was obtained from phenol and hydrogen.

[0514] (Step 2) The cyclohexanone crude liquid 7a obtained from the reaction tower in Step 1 contained unreacted benzene, monochlorobenzene, phenol, etc. The obtained cyclohexanone crude liquid 7a was supplied to a distillation column for the purpose of purification. Thereafter, distillation was repeated a plurality of times to obtain a cyclohexanone-containing treatment liquid (treatment liquid 7A).

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

[0516]

Chem.

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

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

[0519] (Step 2) In Step 1, the PGME crude liquid 8a obtained from the reaction tower contained unreacted methanol, propylene oxide, a catalyst tertiary amine, and the like. For the purpose of purifying the obtained PGME crude liquid 8a, it was fed to a distillation column. Thereafter, distillation was repeated a plurality of times to obtain a PGME-containing treatment liquid (Treatment Liquid 8A).

[0520] The compound (B) contained in the obtained PGME-containing treatment liquid (Treatment Liquid 8A) was the following compound. In each of these compounds, the content rate in the treatment liquid satisfied the requirement (b) (see Table 2).

[0521]

Chemical formula

[0522] <Synthesis Example 9> Synthesis of a treatment liquid (Treatment Liquid 8A) containing MMP (methyl 3-methoxypropionate) (Step 1) By the method described in JP-A-2007-63209, 74.0 g (0.86 mol) of methyl acrylate and potassium t-butoxide (KOt-Bu) as a basic catalyst were weighed and gradually added dropwise from a dropping funnel over about 1 hour. At this time, since heat was generated when a small amount of methyl acrylate was added dropwise, the reaction temperature was controlled to 40 °C while cooling with ice water. After completion of the dropwise addition, heating and stirring were carried out at 40 °C for 1 hour, and the total reaction time was set to 2 hours. Thereafter, phosphoric acid was added, and after confirming neutrality with pH test paper, stirring was carried out at room temperature for 30 minutes. After neutralization, suction filtration was carried out to filter off the solid of the neutralized salt of the catalyst, and 9a of a crude liquid containing MMP (hereinafter referred to as "MMP crude liquid") was obtained.

[0523] (Step 2) In Step 1, the MMP crude liquid 9a obtained from the reaction tower contains unreacted methanol, methyl acrylate, and the like. For the purpose of purifying the obtained MMP crude liquid 9a, it was fed to a distillation column. Thereafter, distillation was repeated a plurality of times to obtain a MMP-containing treatment liquid (treatment liquid 9A).

[0524] Compound (B) contained in the obtained MMP-containing treatment liquid (treatment liquid 9A) was the following compound. All of these compounds satisfied requirement (b) in terms of the content rate in the treatment liquid (see Table 2).

[0525] [Chemical formula]

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

[0527] [Measurement by SP-ICP-MS method] 1) Preparation of standard substances Ultra-pure water was measured and put into a clean glass container, and after adding measurement target metal particles with a median diameter of 50 nm to a concentration of 10,000 particles / ml, the dispersion liquid treated with an ultrasonic cleaner for 30 minutes was used as a standard substance for measuring transport efficiency.

[0528] 2) The SNP-ICP-MS device used Manufacturer: PerkinElmer Model: NexION350S 3) Measurement conditions of SNP-ICP-MS For SNP-ICP-MS, a coaxial nebulizer made of PFA, a cyclone-type spray chamber made of quartz, and a torch injector with an inner diameter of 1 mm made of quartz were used, and the liquid to be measured was aspirated at about 0.2 mL / min. The oxygen addition amount was 0.1 L / min, the plasma output was 1600 W, and cell purging was performed with ammonia gas. The time resolution was analyzed at 50 μs.

[0529] The content rate of metal particles and the content rate of metal atoms were measured using the following analysis software attached to the manufacturer. · Content rate of metal particles: Syngistix nano application module dedicated to "SP-ICP-MS" for nanoparticle analysis · Content rate of metal atoms: Syngistix for ICP-MS software The results are shown in Table 1 below.

[0530] [Measurement of the content rates of compound (A), compound (B) and inorganic substance (C)] For each component used in each example and each comparative example, measurement was carried out by GC / MS (Gas Chromatograph / Mass Spectrometer), LC / MS (Liquid Chromatograph / Mass Spectrometer), NMR (Nuclear magnetic resonance) and IC (Ion Chromatography). The measurement of organic substances was carried out by GC / MS, LC / MS and NMR, and the analysis of inorganic substances was carried out by IC. [GC / MS] (Gas chromatograph mass spectrometer) (Measurement conditions) Apparatus: Manufactured by Shimadzu Corporation, "GCMS-2020" [LC / MS] (Liquid Chromatograph Mass Spectrometer) (Measurement Conditions) Apparatus: Manufactured by Thermo Fisher Scientific "UPLC-H-Class, Xevo G2-XS QTof" [NMR] (Nuclear Magnetic Resonance) (Measurement Conditions) Apparatus: JEOL AL400 type Measured Nucleus: 1 H Solvent: CDCl3 [IC] (Ion Chromatography) (Measurement Conditions) Apparatus: Manufactured by Shimadzu Corporation, "HIC-SP".

[0531] The content rates of each compound are shown in Table 1 below. Note that the columns for "S", "Al", "B", "N", and "K" in the inorganic substance (C) of Table 1 represent the content rates of the inorganic substance containing S, the inorganic substance containing Al, the inorganic substance containing B, the inorganic substance containing N, and the inorganic substance containing K, respectively.

[0532] [Measurement of the dissolution rate (ER) of the resist film] An organic antireflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a silicon wafer, baked at 205 °C for 60 seconds to form an antireflection film with a film thickness of 78 nm. Thereafter, a commercially available product FAiRS-9101A12 (ArF resist composition manufactured by Fujifilm Electronic Materials Co., Ltd.) was applied using a spin coater and baked at 100 °C for 60 seconds. The obtained wafer was subjected to full wafer exposure at 25 [mJ / cm 2 using an ArF excimer laser scanner (NA 0.75). Thereafter, it was heated at 120 °C for 60 seconds. This wafer was cut into 2 cm × 2 cm and immersed in each of the treatment liquids described in Table 1 at 23 °C for 10 minutes. The film thickness before and after immersion was measured using an optical film thickness measuring instrument ellipsometry to calculate the dissolution rate (ER). The results are shown in Table 1.

[0533] [Defect suppression performance (measurement of the number of defects)] Using a wafer surface inspection apparatus (SP-5; manufactured by KLA Tencor), the number of particles with a diameter of 32 nm or more (hereinafter referred to as "defects") present on the surface of a 300-mm diameter silicon substrate was measured. Next, this silicon substrate was set in a spin ejection apparatus and while rotating, various treatment liquids shown in Table 1 were ejected onto the surface of the silicon substrate at a flow rate of 1.5 L / min. Thereafter, a rinsing process was performed and it was dried. Regarding the obtained sample, again using the above apparatus (SP-5), the number of defects present on the surface of the silicon substrate was measured, and the difference from the initial value was taken as the number of defects. The results of evaluating the obtained number of defects based on the following criteria are shown in Table 1. In the following criteria, Evaluation D achieves the defect suppression performance required for a treatment liquid for semiconductor manufacturing.

[0534] A: The number of defects was 50 or less. B: The number of defects exceeded 50 and was 100 or less. C: The number of defects exceeded 100 and was 500 or less. D: The number of defects exceeded 500 and was 1000 or less. E: The number of defects exceeded 1000.

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

[0543] As the purification method, a production apparatus having a structure according to the production apparatus shown in FIG. 2 described above 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 the filtration method, the filters shown in Table 3 below were used as the filters used in the filtration apparatus provided in the above production apparatus to adjust the purity of the treatment liquid.

[0544] Before purifying the crude liquid 7a by the above purification method, the above production apparatus was washed with a cleaning liquid. As the cleaning method, treatment liquid 7E (cyclohexanone) shown in Table 1 was used as the cleaning liquid, and this treatment liquid 7E was passed through the above filter 10 times in circulation, and this was repeated 3 sets as one set.

[0545]

Table 3

[0546] In Table 3, Nylon, PTFE (polytetrafluoroethylene), and UPE (Ultra High Molecular Weight Polyethylene) represent filters mainly composed of nylon, filters mainly composed of PTFE, and filters mainly composed of UPE, respectively. Also, in IEX-PTFE sufric acid and IEX-PTFE carboxylic acid, IEX indicates an ion exchange group, and refers to filters in which the surface of PTFE is modified with sulfonic acid or carboxylic acid, respectively.

[0547] <Fabrication of Resist Pattern> [Examples 101 to 112, Comparative Examples 101, 102] An organic antireflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a silicon wafer, baked at 205 °C for 60 seconds to form an antireflection film with a film thickness of 78 nm. Then, a commercially available product FAiRS-9101A12 (ArF resist composition manufactured by Fujifilm Electronic Materials Co., Ltd.) was applied using a spin coater, baked at 100 °C for 60 seconds to form a resist film with a film thickness of 150 nm. The obtained wafer was subjected to pattern exposure at 25 [mJ / cm 2 using an ArF excimer laser scanner (NA 0.75). Then, after heating at 120 °C for 60 seconds, development (negative development) was performed for 30 seconds with each processing solution described in Table 4 to obtain an L / S pattern.

[0548] For Examples 105 to 107, after the above development, rinsing was performed for 30 seconds using each processing solution described in Table 4 to obtain an L / S pattern.

[0549] [Examples 113 to 119] An organic antireflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a silicon wafer, baked at 205°C for 60 seconds to form an antireflection film with a film thickness of 78 nm. Then, in order to improve the coatability, a pre-wet process of applying the treatment liquid described in Table 3 in advance was performed. Thereafter, a commercially available product FAiRS-9101A12 (ArF resist composition manufactured by Fujifilm Electronic Materials Co., Ltd.) was applied using a spin coater, baked at 100°C for 60 seconds to form a resist film with a film thickness of 150 nm. The obtained wafer was pattern-exposed at 25 [mJ / cm 2 using an ArF excimer laser scanner (NA 0.75). Then, after heating at 120°C for 60 seconds, it was developed for 30 seconds (negative development) with the treatment liquid described in Table 4, and the obtained pattern was rinsed and washed with the treatment liquid described in Table 1 to obtain an L / S pattern.

[0550] [Lithography performance] After pattern formation, the upper surface of the line pattern and the space portion were observed using a length measurement scanning electron microscope (S9380II manufactured by Hitachi, Ltd.). The smaller the value of the formed pattern dimension, the better the performance. According to the following criteria, Evaluation D indicates that the lithography performance required for the resist pattern is achieved. The evaluation results are shown in Table 4.

[0551] A L / S < 80 nm B 80 nm ≤ L / S < 120 nm C 120 nm ≤ L / S < 150 nm D 150 nm ≤ L / S < 200 nm E L / S ≥ 200 nm

[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-A-2007-254168. After confirming that the contents of Na, Ca, and Fe were each less than 10 mass ppb, it was used for the preparation of the treatment liquid.

[0554] Example 201 90.5 parts by mass of the liquid of treatment liquid 1A of Example 1 and 9.5 parts by mass of the dimethyl sulfoxide obtained above were mixed to prepare treatment liquid X-1. In addition to treatment liquid 1A and the above dimethyl sulfoxide, treatment liquid X-1 contains two or more compounds (B) that satisfy requirement (b) and an inorganic substance (C), and the total content rate of compound (B) is 10 -10 ~0.1 mass%, and the ratio P of the compound (B) represented by formula I to the inorganic substance (C) is 10 3 ~10 -6 When the same evaluation as in Example 1 and Example 101 was performed using this treatment liquid 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 95 parts by mass of the liquid of treatment liquid 1A of Example 1 and 5 parts by mass of the dimethyl sulfoxide obtained above were mixed to prepare treatment liquid X-2.

[0556] In addition to treatment liquid 1A and the above dimethyl sulfoxide, treatment liquid X-2 contains two or more compounds (B) that satisfy requirement (b) and an inorganic substance (C), and the total content rate of compound (B) is 10 -10 ~0.1 mass%, and the ratio P of the compound (B) represented by formula I to the inorganic substance (C) is 10 3 ~10 -6 When the same evaluation as in Example 1 and Example 101 was performed using this treatment liquid 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 85 parts by mass of the liquid of the treatment liquid 1A of Example 1 and 15 parts by mass of the dimethyl sulfoxide obtained above were mixed to prepare a treatment liquid X-3. When the same evaluations as in Example 1 and Example 101 were carried out using this treatment liquid X-3, the same results as in Example 1 were obtained, but there was remaining treatment liquid after rinsing and it took time to dry.

[0558] <Examples 301 to 307> The first treatment liquid and the second treatment liquid shown in Table 5 below were mixed at the ratios shown in the same table to prepare treatment liquids 101 to 106. Further, the treatment liquid 107 shown in Table 5 is the treatment liquid 9A prepared above. For these treatment liquids 101 to 107, the defect suppression performance was evaluated in the same manner as the method described above. In addition, the resist saving property when these treatment liquids were used as a pre-wet liquid was evaluated. Further, the performance when these treatment liquids were used as a rinse liquid after ashing or p-CMP was evaluated. The results are shown in Table 5.

[0559] [Resist saving property] The resist saving property when each treatment liquid was used as a pre-wet solution was evaluated by the following method. In this specification, having excellent resist saving property means a state having excellent uniformity and excellent film thickness controllability, and it can be understood that this can suppress the deterioration of lithography performance and the occurrence of defects. The resist composition 1 used is as follows.

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

[0561] [Chemical formula]

[0562] The weight average molecular weight (Mw) of the above acid-decomposable resin is 7500, and the numerical values described in each repeating unit mean mol%.

[0563] The photoacid generator shown below: 8 parts by mass

[0564]

Chem.

[0565] The following 4 kinds of quenchers: 5 parts by mass (total)

[0566]

Chem.

[0567] The mass ratio of the above quenchers is, in order from the left, 0.1:0.3:0.3:0.2. Among the above 4 kinds of quenchers, the one on the right side is a polymer type with a weight average molecular weight (Mw) of 5000. Also, the numerical values described in each repeating unit mean molar ratio.

[0568] The following 2 kinds of hydrophobic resins: 4 parts by mass (total)

[0569]

Chem.

[0570] The mass ratio of the above hydrophobic resins is, in order from the left, 0.5:0.5. Among the above 2 kinds of hydrophobic resins, the hydrophobic resin on the left has a weight average molecular weight (Mw) of 7000, and the weight average molecular weight (Mw) of the hydrophobic resin on the right is 8000. Also, in each hydrophobic resin, the numerical values described in each repeating unit mean molar ratio.

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

[0572] <Resist Composition 2> A resist composition 2 was prepared under the same conditions as resist composition 1, except that the above solvent 1 (PGMEA: CyHx: GBL = 3 parts by mass: 600 parts by mass: 100 parts by mass) was replaced with the following solvent 2.

[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 Pure Chemical Industries, Ltd.): 100 parts by mass.

[0574] <Homogeneity> First, as a control, the above resist composition 1 (or resist composition 2) was directly applied onto a silicon wafer with an anti-reflection film and a diameter of about 30 cm (12 inches). For the application, a spin coater (trade name "LITHIUS", manufactured by Tokyo Electron Limited) was used. The obtained resist film was baked at 90°C. Regarding the baked resist film, a 59-point map measurement was performed using a film thickness measurement device Lambda Ace manufactured by Dainippon Screen Mfg. Co., Ltd. to confirm that no coating spots occurred. Note that the coating spots refer to a state where, when 59 measurement points are extracted circularly from the resist film to be measured and the measurement results of the resist film thickness at each measurement point are arranged two-dimensionally for each measurement point and observed, there is no unevenness in the thickness of the resist film.

[0575] Next, a silicon wafer with an anti-reflection film and a diameter of about 30 cm (12 inches) was separately prepared, and each treatment liquid was dropped. Then, the same amount of resist composition 1 (or resist composition 2) as the control was applied and baked at 90°C. Regarding the obtained resist film, it was observed in the same manner as above to confirm that no coating spots occurred. Next, the resist composition 1 (or resist composition 2) to be used was reduced to 50% by mass and 30% by mass of the control, and the same test as above was conducted to examine whether coating spots occurred. The results were evaluated according to the following criteria, and the results are shown in Table 5.

[0576] AA: When the usage amount of the resist composition was reduced to 30% by mass and 50% by mass of the control, no coating marks occurred in either case. A: Even when the usage amount of the resist composition was reduced to 50% by mass of the control, no coating marks occurred. However, when the usage amount was reduced to 30% by mass of the control, coating marks occurred. B: When the usage amount of the resist composition was reduced to 30% by mass and 50% by mass of the control, coating marks occurred in both cases.

[0577] <Film thickness controllability> Each processing liquid was dropped onto a silicon wafer with a diameter of about 30 cm (12 inches) equipped with an antireflection film. Then, the resist composition 1 (or resist composition 2) was directly applied so that the thickness of the resulting resist film would be 8.5 nm. For the application, a spin coater (trade name "LITHIUS", manufactured by Tokyo Electron Limited) was used. The obtained resist film was baked at 90°C. For the baked resist film, 59-point map measurement was performed using a film thickness measuring device Lambda Ace manufactured by Dainippon Screen Mfg. Co., Ltd., and the standard deviation of the thickness of the resist film (hereinafter also referred to as "σ") was determined. Next, 3σ was determined from the standard deviation. The results were evaluated according to the following criteria and shown in Table 5.

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

[0579] 〔Rinse performance after ashing removal〕 A 12-inch wafer with a resist film (film thickness: 0.5 μm) prepared by applying Resist Composition 1 (or Resist Composition 2) onto a silicon wafer, followed by exposure (50 mJ) and heat drying (220 °C) was prepared. Next, the above resist film was removed by ashing using a plasma gas under the following conditions. Subsequently, each treatment liquid shown in Table 5 (Treatment Liquids 101 to 107) was used for washing to remove the residue (ashing residue) after ashing removal. Thereafter, using SP-2 (manufactured by KLA TENCOL), the number of defects on the wafer after washing was counted to evaluate the rinsing performance of each treatment liquid with respect to the ashing residue. [Ashing Removal Conditions] Wafer Temperature: 250 °C O 2 Gas Flow Rate: 1,000 sccm Pressure: 70 Pa, Microwave Output: 1 kW -Evaluation Criteria- AA: The number of defects was 50 or less. A: The number of defects exceeded 50 and was 80 or less. B: The number of defects exceeded 80 and was 100 or less. C: The number of defects exceeded 100 and was 150 or less. D: The number of defects exceeded 150.

[0580] [Rinsing Performance after p-CMP] The surface of a 12-inch Sematech 845 (copper wiring, barrier metal TaN, oxide film TEOS; manufactured by Sematech) was polished and planarized using CSL9044C (slurry manufactured by FFPS). Thereafter, finish polishing was performed using BSL8178C (slurry manufactured by FFPS). Next, after washing with Clean100 (manufactured by Wako Pure Chemical Industries), each treatment liquid was used as a rinsing liquid. Thereafter, using a pattern defect inspection apparatus (ComPLUS manufactured by AMAT), the number of defects on the pattern of the above Sematech 854 was measured. 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 exceeded 50 and was 80 or less. B: The number of defects exceeded 80 and was 100 or less. C: The number of defects exceeded 100 and was 150 or less. D: The number of defects exceeded 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) satisfying 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, comprising: 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 method of 0.001 to 100 ppt by mass. 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 compound (A) is propylene glycol monomethyl ether acetate, 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 compound (A) is cyclohexanone, 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 treatment 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, Q = [total mass of compound (A)] / [total mass of compound (B)] Formula II

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

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

9. The processing liquid for semiconductor manufacturing according to any one of claims 1 to 6, wherein the processing liquid for semiconductor manufacturing is a pre-wetting liquid.

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