Method for stabilizing photoacid generators

Abstract

This application relates to a method for stabilizing a photoacid generating agent in a photoresist composition, a photoresist composition, and the use of the photoresist composition.

Description

Technical Field

[0001] This application relates to a method for stabilizing a photoacid generating agent in a photoresist composition, a photoresist composition, and the use of the photoresist composition. Background Technology

[0002] When attempting to form intricate patterns using photolithography, high-resolution photoresist materials are required. To meet this need, a chemically amplified photoresist composition is typically used, which comprises a base resin and a photoacid generating agent.

[0003] For example, a chemically amplified positive photoresist composition comprises a resin component and a photoacid generating agent. The solubility of the resin component in an alkaline aqueous solution increases due to the action of acid, and the photoacid generating agent generates acid under light irradiation. After the photoresist pattern is formed, the exposed portion dissolves in the alkali when the photoacid generating agent produces acid.

[0004] Patent Document 1 describes a method for producing a photoresist composition, comprising the steps of: preparing an organic solvent (S) using ethyl lactate containing an antioxidant, such that the concentration of the antioxidant in the organic solvent (S) is 10 ppm or higher, and dissolving a base material component in the organic solvent (S).

[0005] Patent document 2 describes a method comprising:

[0006] A layered structure is provided, the layered structure including a photoresist layer disposed on the surface of a substrate, the photoresist layer including the PAG polymer of claim 13;

[0007] The resist layer is irradiated in a patterned manner to form an exposed resist layer;

[0008] The exposed resist layer is baked at a temperature of about 90 degrees Celsius to about 130 degrees Celsius for at least 1 second to form a treated resist layer; and

[0009] A portion of the treated resist layer is selectively removed using a developer, thereby forming a patterned resist layer.

[0010] Existing technical documents

[0011] Patent documents

[0012] [Patent Document 1] US2009-155713A

[0013] [Patent Document 2] US2018-044459A Summary of the Invention

[0014] The inventors have recently discovered that one or more important issues still need improvement, specifically: decomposition of the photoacid generator in the photoresist composition; decomposition of the photoacid generator due to reaction with the solvent; decomposition of the photoacid generator due to reaction with the quencher in the presence of amines without ultraviolet light irradiation; reduced standing wave in the resist pattern when the bottom antireflective coating is not formed; uneven width of the resist pattern; insufficient rectangularity of the resist pattern; insufficient resolution of the resist pattern; insufficient heat resistance of the resist pattern; and insufficient manufacturing process efficiency.

[0015] The inventors have discovered that these problems can be solved by providing the methods disclosed and claimed below.

[0016] This invention relates to a method for stabilizing a photoacid-generating agent in a photoresist composition, the method comprising step (a), mainly comprising step (a), or comprising step (a):

[0017] (a) A mixture of multiple compounds to form a photoresist composition, wherein the multiple compounds comprise a polymer, a photoacid generator, an amine, and compound A represented by formula (I):

[0018] (I)

[0019] Where R 1 To R 5 Each independently represents H and C. 1-20 Alkyl, C 1-20 Alkoxy, OH or NH2, preferably H or C 1-10 Alkyl or OH, more preferably H or OH;

[0020] When R 1 To R 5 When each is an alkyl group independently, one or more non-adjacent CH2 groups may be optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CR=CR-, or -C≡C-.

[0021] The present invention also relates to a photoresist composition comprising, being mainly composed of, or being composed of: a polymer, a photoacid generating agent, compound A represented by formula (I), and an amine;

[0022] The molar ratio of compound A to amine is in the range of 0.1 to 10, preferably 0.2 to 8, more preferably 0.3 to 5, and most preferably 0.5 to 3.

[0023] Preferably, based on 100 parts by weight of the polymer, the amine content is in the range of 0.1 to 1 part by weight, more preferably 0.2 to 0.9 parts by weight, and most preferably 0.3 to 0.8 parts by weight.

[0024] (I)

[0025] Where R 1 To R 5 Each independently represents H and C. 1-20 Alkyl, C 1-20 Alkoxy, OH or NH2, preferably H, C 1-10 Alkyl, C 1-10 Alkyl group or OH, more preferably H or OH;

[0026] When R 1 To R 5 When each is an alkyl group independently, one or more non-adjacent CH2 groups may be optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CR=CR-, or -C≡C-.

[0027] The present invention also relates to the use of compound A, represented by formula (I), for stabilizing photoacid-generating agents in photoresist compositions:

[0028] (I)

[0029] Where R 1 To R 5 Each independently represents H and C. 1-20 Alkyl, C 1-20 Alkoxy, OH or NH2, preferably H or C 1-10 Alkyl or OH, more preferably H or OH;

[0030] When R 1 To R 5 When each is an alkyl group independently, one or more non-adjacent CH2 groups may be optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CR=CR-, or -C≡C-.

[0031] Technical effects of the invention

[0032] This invention provides one or more of the following effects: inhibiting the decomposition of photoacid generating agents in photoresist compositions; inhibiting reactions between photoacid generating agents and solvents that lead to the decomposition of photoacid generating agents; inhibiting reactions between photoacid generating agents and solvents in the presence of amines that lead to the decomposition of photoacid generating agents; inhibiting reactions between photoacid generating agents and solvents in the presence of tertiary amines that lead to the decomposition of photoacid generating agents; sufficiently reducing standing waves in the resist pattern even without forming a bottom anti-reflective coating; achieving uniform resist pattern width; sufficient rectangularity of the resist pattern; sufficient resolution of the resist pattern; sufficient heat resistance of the resist pattern; and sufficient manufacturing process efficiency.

[0033] [Term Definitions]

[0034] Unless otherwise specified, the definitions or examples set forth in this paragraph shall apply in this specification.

[0035] The singular form includes the plural form; "a" or "the" means "at least one." An element in a concept can be expressed in multiple types, and when describing its quantity (e.g., mass% or mole%), the quantity refers to the sum of the multiple types. "And / or" includes all combinations of elements, as well as cases where the element is used alone.

[0036] When using "~ / to" or "-" to represent a numerical range, it includes both endpoints and the units are the same. For example, 5 to 25 mol% means more than 5 mol% and less than 25 mol%.

[0037] Such as "C" x-y “C” x -C y "and "C x Descriptions like "" indicate the number of carbon atoms in a molecule or substituent. For example, C 1-6 Alkyl refers to an alkyl chain having one or more but no more than six carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

[0038] When a polymer has multiple repeating units, these repeating units will copolymerize. The copolymerization of these repeating units can be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. When a polymer or resin is represented by a structural formula, the symbols such as n and m outside the parentheses indicate the number of repeating units.

[0039] Temperature is measured in Celsius. For example, 20 degrees means 20 degrees Celsius.

[0040] Additives refer to compounds that have a specific function (e.g., a base-generating agent is a compound capable of generating a base). An embodiment may also exist in which the compound is dissolved or dispersed in a solvent and added to the composition. Preferably, as an embodiment of the invention, the solvent is included as solvent (C) or as another component in the composition according to the invention. Detailed Implementation

[0041] The embodiments of the present invention will now be described in detail.

[0042] [Method for stabilizing photoacid-generating agents in photoresist compositions]

[0043] The method for stabilizing a photoacid generator in a photoresist composition according to the present invention (hereinafter referred to as the method) comprises step (a), mainly consists of step (a), or consists of step (a):

[0044] (a) A mixture of multiple compounds is used to form a photoresist composition, wherein the multiple compounds comprise a polymer, a photoacid generator, an amine, and compound A represented by formula (I):

[0045] (I)

[0046] Where R 1 To R 5 Each independently represents H and C. 1-20 Alkyl, C 1-20 Alkoxy, OH or NH2, preferably H or C 1-10 Alkyl or OH, more preferably H or OH;

[0047] When R 1 To R 5 When each is an alkyl group independently, one or more non-adjacent CH2 groups may be optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CR=CR-, or -C≡C-.

[0048] Step (a)

[0049] In step (a), the multiple compounds do not need to be mixed in a specific order. The multiple compounds may or may not be mixed with a solvent.

[0050] In some embodiments of the invention, step (a) comprises, consists primarily of, or consists of the following steps in this order:

[0051] (a1) The polymer is mixed with a photoacid generating agent to form a first mixture.

[0052] (a2) The first mixture obtained in step (a1) is mixed with an amine to form a second mixture, and

[0053] (a3) Mix the second mixture obtained in step (a2) with compound A represented by formula (I).

[0054] In some embodiments of the invention, step (a) comprises, consists primarily of, or consists of the following steps in this order:

[0055] (a1) The polymer is mixed with a photoacid generating agent to form a first mixture.

[0056] (a2) The first mixture obtained in step (a1) is mixed with compound A represented by formula (I) to form a second mixture, and

[0057] (a3) Mix the second mixture obtained in step (a2) with an amine.

[0058] In some embodiments of the invention, step (a) comprises, consists primarily of, or consists of the following steps in this order:

[0059] (a1) The polymer is mixed with an amine to form a first mixture.

[0060] (a2) The first mixture obtained in step (a1) is mixed with a photoacid generating agent to form a second mixture, and

[0061] (a3) Mix the second mixture obtained in step (a2) with compound A represented by formula (I).

[0062] In some embodiments of the invention, step (a) comprises, consists primarily of, or consists of the following steps in this order:

[0063] (a1) The polymer is mixed with an amine to form a first mixture.

[0064] (a2) The first mixture obtained in step (a1) is mixed with compound A represented by formula (I) to form a second mixture, and

[0065] (a3) Mix the second mixture obtained in step (a2) with the photoacid generating agent.

[0066] In some embodiments of the invention, step (a) comprises, consists primarily of, or consists of the following steps in this order:

[0067] (a1) The polymer is mixed with compound A represented by formula (I) to form a first mixture.

[0068] (a2) The first mixture obtained in step (a1) is mixed with an amine to form a second mixture, and

[0069] (a3) Mix the second mixture obtained in step (a2) with the photoacid generating agent.

[0070] In some embodiments of the invention, step (a) comprises, consists primarily of, or consists of the following steps in this order:

[0071] (a1) The polymer is mixed with compound A represented by formula (I) to form a first mixture.

[0072] (a2) The first mixture obtained in step (a1) is mixed with a photoacid generating agent to form a second mixture, and

[0073] (a3) Mix the second mixture obtained in step (a2) with an amine.

[0074] In some embodiments of the invention, step (a) comprises, consists primarily of, or consists of the following steps in this order:

[0075] (a1) The photoacid generating agent is mixed with an amine to form a first mixture.

[0076] (a2) The first mixture obtained in step (a1) is mixed with compound A represented by formula (I) to form a second mixture, and

[0077] (a3) Mix the second mixture obtained in step (a2) with the polymer.

[0078] In some embodiments of the invention, step (a) comprises, consists primarily of, or consists of the following steps in this order:

[0079] (a1) The photoacid generating agent is mixed with an amine to form a first mixture.

[0080] (a2) The first mixture obtained in step (a1) is mixed with a polymer to form a second mixture, and

[0081] (a3) Mix the second mixture obtained in step (a2) with compound A represented by formula (I).

[0082] In some embodiments of the invention, step (a) comprises, consists primarily of, or consists of the following steps in this order:

[0083] (a1) The photoacid generating agent is mixed with compound A represented by formula (I) to form a first mixture.

[0084] (a2) The first mixture obtained in step (a1) is mixed with a polymer to form a second mixture, and

[0085] (a3) Mix the second mixture obtained in step (a2) with an amine.

[0086] In some embodiments of the invention, step (a) comprises, consists primarily of, or consists of the following steps in this order:

[0087] (a1) The photoacid generating agent is mixed with compound A represented by formula (I) to form a first mixture.

[0088] (a2) The first mixture obtained in step (a1) is mixed with an amine to form a second mixture, and

[0089] (a3) Mix the second mixture obtained in step (a2) with the polymer.

[0090] In some embodiments of the invention, step (a) comprises, consists primarily of, or consists of the following steps in this order:

[0091] (a1) The amine is mixed with compound A represented by formula (I) to form a first mixture.

[0092] (a2) The first mixture obtained in step (a1) is mixed with a polymer to form a second mixture, and

[0093] (a3) Mix the second mixture obtained in step (a2) with the photoacid generating agent.

[0094] In some embodiments of the invention, step (a) comprises, consists primarily of, or consists of the following steps in this order:

[0095] (a1) The amine is mixed with compound A represented by formula (I) to form a first mixture.

[0096] (a2) The first mixture obtained in step (a1) is mixed with a polymer to form a second mixture, and

[0097] (a3) Mix the second mixture obtained in step (a2) with the photoacid generating agent.

[0098] In some embodiments of the present invention, it consists primarily of the following steps in this order, or consists of the following steps:

[0099] (a1) The polymer, photoacid generating agent, and amine are simultaneously mixed to form a first mixture, and

[0100] (a2) Mix the first mixture obtained in step (a1) with compound A represented by formula (I).

[0101] In some embodiments of the invention, step (a) comprises, consists primarily of, or consists of the following steps in this order:

[0102] (a1) The polymer, the photoacid generating agent, and compound A represented by formula (I) are simultaneously mixed to form a first mixture, and

[0103] (a2) Mix the first mixture obtained in step (a1) with an amine.

[0104] In some embodiments of the invention, step (a) comprises, consists primarily of, or consists of the following steps in this order:

[0105] (a1) The polymer, amine, and compound A represented by formula (I) are simultaneously mixed to form a first mixture, and

[0106] (a2) Mix the first mixture obtained in step (a1) with the photoacid generating agent.

[0107] In some embodiments of the invention, step (a) comprises, consists primarily of, or consists of the following steps in this order:

[0108] (a1) A photoacid generating agent, an amine, and compound A represented by formula (I) are simultaneously mixed to form a first mixture, and

[0109] (a2) Mix the first mixture obtained in step (a1) with the polymer.

[0110] In some embodiments of the invention, step (a) comprises, consists primarily of, or consists of the following steps in this order:

[0111] (a1) The polymer, photoacid generating agent, compound A represented by formula (I) and amine are mixed simultaneously.

[0112] According to the invention, it is preferable to mix the amine with compound A at least first in step (a1). In the preferred embodiment, the remaining compounds may be mixed simultaneously with the amine and compound A, or they may be mixed separately, without following a specific order.

[0113] Not bound by theory, but believed to be that mixing the amine with compound A at least first can more effectively suppress the decomposition of photoacid generating agents.

[0114] In another preferred embodiment, at least the amine and compound A can be first mixed with a solvent to form an amine solution and a compound A solution, respectively.

[0115] In another preferred embodiment, at least the amine and compound A can be mixed simultaneously with the solvent to form a first mixture.

[0116] Not bound by theory, but believed to be that mixing the amine and compound A with the solvent at least first can make the amine and compound A mix more thoroughly. Therefore, it is believed that the decomposition of the photoacid-generating agent can be suppressed more effectively.

[0117] Therefore, step (a1) may include the following steps (a1') and (a2') or the following step (a1'').

[0118] (a1') The amine and compound A are respectively mixed with a solvent to form an amine solution and a compound A solution, and

[0119] (a2') The amine solution is mixed with the compound A solution to form a first mixture.

[0120] (a1'') The amine and compound A are mixed simultaneously with a solvent to form a first mixture.

[0121] In addition to the polymer, photoacid generator, amine, and compound A represented by formula (I), the mixture may contain one or more other compounds (hereinafter referred to as other compounds) and be mixed with the polymer, photoacid generator, amine, and compound A represented by formula (I). There is no specific requirement for the mixing order of these other compounds.

[0122] Multiple compounds can be mixed using known methods. For example, multiple compounds can be stirred using a stirring rod or a stirrer with blades, propellers, or turbines. One or more of the multiple compounds can be intermittently added dropwise to another compound or a mixture of two or more compounds within a predetermined time and a certain temperature range. During the mixing process, the temperature can be moderately increased or decreased.

[0123] The preset time is preferably between 1 and 120 minutes, more preferably between 1 and 90 minutes, very preferably between 1 and 60 minutes, and even more preferably between 1 and 30 minutes. The temperature range is preferably between 1 and 90°C, more preferably between 5 and 60°C, very preferably between 10 and 40°C, and even more preferably between 15 and 30°C.

[0124] Compound A

[0125] These compounds contain compound A. While not strictly theoretical, compound A is believed to stabilize photoacid generators. It is thought that photoacid generators decompose in the presence of amines, and compound A inhibits this decomposition.

[0126] Compound A is represented by formula (I):

[0127] (I)

[0128] Where R 1 To R 5 Each independently represents H and C. 1-20 Alkyl, C 1-20 Alkoxy, OH or NH2, preferably H, containing C 1-20 Alkyl groups, linear, branched or cyclic structures, containing C 1-20 The alkoxy group has a linear, branched, or cyclic structure, or OH, more preferably H, and contains C. 1-10 Alkyl groups, linear, branched or cyclic structures, containing C 1-10 The alkoxy group has a linear, branched, or cyclic structure, or OH, with H or OH being the most preferred.

[0129] When R 1 To R 5When each is an alkyl group independently, one or more non-adjacent CH2 groups may be optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CR=CR- or -C≡C-, preferably not replaced.

[0130] Preferably, R 1 To R 5 At least one of them is OH, more preferably, R 1 and R 5 At least one of them is OH, very preferably, R 1 Or R 5 It is OH.

[0131] Preferably, R 1 To R 5 At least one of them is H, more preferably, R 2 To R 4 At least one of them is H, very preferably, R 2 To R 4 For H.

[0132] Exemplary examples of compound A are selected from one or more members of the following group:

[0133]

[0134]

[0135]

[0136] The molecular weight of compound A is preferably in the range of 10 to 1000, more preferably 30 to 800, very preferably 50 to 500, and most preferably in the range of 100 to 300. The molecular weight of compound A can be determined by known methods, such as freezing point depression and vapor pressure depression.

[0137] Based on 100 parts by mass of the polymer, the content of compound A is preferably 0.01 to 1 part by mass, more preferably 0.05 to 0.8 parts by mass, and very preferably 0.07 to 0.5 parts by mass.

[0138] The molar ratio of compound A to amine is preferably from 0.1 to 10, more preferably from 0.2 to 8, very preferably from 0.3 to 5, and most preferably from 0.5 to 3.

[0139] Not bound by theory, but it is believed that when the molar ratio of compound A to amine is within the above range, compound A can further sufficiently suppress the decomposition of photoacid generating agent.

[0140] amine

[0141] These compounds contain an amine. In a preferred embodiment, the amine is selected from one or more members of the group consisting of primary amines, secondary amines, and tertiary amines. More preferably, the amine is a tertiary amine.

[0142] Primary amines may be selected from one or more members of the group consisting of: ethylamine, propylamine, butylamine, 2-ethylhexylamine, octylamine, dodecylamine, n-octylamine, n-decylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, and oleylamine.

[0143] The secondary amine may be selected from one or more members of the group consisting of: dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, bis-2-ethylhexylamine, methylethylamine, ethylbutylamine, N-methyl-1-aminocyclohexane, ethylpentylamine, piperidine, piperazine, and morpholine.

[0144] The tertiary amine may be selected from one or more members of the group consisting of: trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine and tri-dodecanamine, more preferably from one or more members of the group consisting of tri-n-heptylamine, tri-n-octylamine and tri-n-nonylamine.

[0145] Based on 100 parts by weight of the polymer, the content of the amine is preferably in the range of 0.1 to 1 part by weight, more preferably 0.2 to 0.9 parts by weight, and most preferably in the range of 0.3 to 0.8 parts by weight.

[0146] The molecular weight of the amine is preferably in the range of 30 to 1000, more preferably 100 to 800, very preferably 150 to 600, and most preferably 200 to 500.

[0147] Photoacid generator

[0148] These compounds contain photoacid generating agents. In a preferred embodiment, the photoacid generating agent is represented by formula (A-1).

[0149] B n+ Cation B n- Anion (A-1)

[0150] Among them, B n+ The cation is preferably a cation represented by formula (AC1), a cation represented by formula (AC2), or a cation represented by formula (AC3). B n+ The cation has an overall valence of n. n is 1 to 3, preferably 1 or 2, and more preferably 1.

[0151] B n- The anion is preferably an anion represented by formula (AA1), formula (AA2), or formula (AA3). n-The anion is n-valent overall. n is 1 to 3, preferably 1 or 2, and more preferably 1.

[0152] Equation (AC1) is as follows:

[0153] (AC1)

[0154] Where R 1 and R 2 Each independently is C 1-20 Alkyl, C 1-20 Aryl or C 1-20 Aryl alkyl group, preferably containing C 1-20 Alkyl, C 1-20 Aryl or C 1-20 Aryl alkyl groups have linear, branched, or cyclic structures, more preferably containing C. 1-15 Aryl or C 1-15 Aryl alkyl group, preferably containing C 1-10 Aryl.

[0155] Preferably, the cation represented by formula (AC1) can also be represented by formula (AC1-1);

[0156] (AC1-1)

[0157] Where R a1 and R a2 Each independently contains C 1-6 Alkyl groups have linear, branched, or cyclic structures containing C 1-6 Alkoxy or C 6-12 The aryl group has a linear, branched, or cyclic structure, preferably a branched C group. 4-6 Alkyl group, more preferably tert-butyl or 1,1-dimethylpropyl, very preferably tert-butyl. na1 and na2 are each independently 0, 1, 2 or 3, preferably 1 each.

[0158] An exemplary example of equation (AC1) is as follows:

[0159]

[0160] Equation (AC2) is as follows:

[0161] (AC2)

[0162] Where R a3 To R a5 Each independently contains C 1-6 Alkyl groups have linear, branched, or cyclic structures containing C 1-6 Alkoxy, C 6-12 Aryl, C 6-12 Aryl thiols or C 6-12The aryloxy group is preferably methyl, ethyl, tert-butyl, methoxy, ethoxy, phenylthio, or phenoxy, and more preferably tert-butyl, methoxy, ethoxy, phenylthio, or phenoxy.

[0163] Each of na3 to na5 is independently 0, 1, 2, or 3. A preferred embodiment is that each of na3 to na5 is 1 and Ra3 to Ra5 ​​are identical. A further preferred embodiment is that each of na3 to na5 is 0.

[0164] An exemplary example of equation (AC2) is as follows:

[0165]

[0166]

[0167] Equation (AC3) is as follows:

[0168] (AC3)

[0169] Where R a6 Each independently contains C 1-6 Alkyl groups have linear, branched, or cyclic structures containing C 1-6 Alkoxy or C 6-12 The aryl group has a linear, branched, or cyclic structure, preferably methyl, ethyl, methoxy, or ethoxy, more preferably methyl or methoxy.

[0170] R a7 and R a8 Each independently contains C 1-6 The alkyl group has a linear, branched, or cyclic structure, preferably methyl, ethyl, or linear butyl, more preferably methyl. na6 to na8 are each independently 0, 1, 2, or 3; more preferably 1 or 3.

[0171] An exemplary example of equation (AC3) is as follows:

[0172]

[0173] Equation (AA1) is as follows:

[0174] (AA1)

[0175] Where R a9 For containing C 1-6 Fluorinated alkyl groups have linear, branched, or cyclic structures containing C 1-6 Fluorinated alkoxy groups, C 6-12 Fluorinated aryl, C 2-12 Fluorine-substituted acyl groups or C 6-12 Fluorine-substituted alkoxyaryl groups have linear, branched, or cyclic structures, preferably containing C. 2-6 Fluorinated alkyl or C6-10 Fluorine-substituted aryl groups have linear, branched, or cyclic structures, with linear C being more preferred. 2-4 Fluorinated alkyl or C 6-8 Fluorinated aryl groups are preferred, with linear C4 fluorosubstituted alkyl groups or C7 fluorosubstituted aryl groups being highly preferred. In R a9 In fluorinated alkyl groups, it is preferable to have all hydrogen atoms in the alkyl moiety replaced by fluorine atoms (hereinafter, the state in which all hydrogen atoms in the group are replaced by fluorine atoms is referred to as "complete fluorination").

[0176] R a9 Preferably, it is a fully fluorinated methyl, ethyl, propyl, butyl, pentyl or toluene (wherein the methyl group is fully fluorinated); more preferably, it is a fully fluorinated propyl, butyl, pentyl or toluene (wherein the methyl group is fully fluorinated); very preferably, it is a fully fluorinated butyl or toluene (wherein the methyl group is fully fluorinated).

[0177] na9 is 1 or 2, preferably 1. When na9 is 2, R a9 It becomes divalent, R a9 The hydrogen or fluorine in it forms a single bond and combines with the S atom.

[0178] An exemplary example of formula (AA1) is as follows:

[0179] CF3SO3 - C3F7SO3 - C4F9SO3 - ,

[0180]

[0181]

[0182] Equation (AA2) is as follows:

[0183] (AA2)

[0184] R a10 To R a12 Each independently contains C 1-6 Fluorinated alkyl groups have linear, branched, or cyclic structures containing C 1-6 Fluorinated alkoxy groups have linear, branched, or cyclic structures containing C 1-6 Alkyl groups have linear, branched, or cyclic structures, preferably containing C. 1-6 Linear, branched, or cyclic structures of fully fluorinated alkyl groups, more preferably linear or branched C 1-6 Fully fluorinated alkyl groups, very preferably fully fluorinated methyl, ethyl or tert-butyl, and most preferably fully fluorinated methyl.

[0185] An exemplary example of equation (AA2) is as follows:

[0186]

[0187] Equation (AA3) is as follows:

[0188] (AA3)

[0189] R a13 It contains C 1-6 Alkylene or C 6-12 The arylene group has a linear, branched, or cyclic structure, preferably methylene, ethylene, propylene, or butylene, more preferably methylene or ethylene, and very preferably methylene.

[0190] na13 can be 0 or 1, preferably 0.

[0191] na23 is 1, 2 or 3, preferably 1 or 2, more preferably 1.

[0192] An exemplary example of equation (AA3) is as follows:

[0193]

[0194] Photoacid generating agents can also be represented by formula (AD).

[0195] (AD)

[0196] R na14 and R na15 Each independently contains C 1-6 Alkyl or C 6-12 The aryl group has a linear, branched, or cyclic structure, preferably containing C. 2-6 Alkyl or C 6-10 The aryl group has a linear, branched, or cyclic structure, more preferably containing C. 4-6 Alkyl or C 6-8 Aryl groups have branched or cyclic structures.

[0197] An exemplary example of the formula (AD) is as follows:

[0198]

[0199] The photoacid generator preferably contains a cation represented by formula (AC1) or (AC2) and an anion represented by formula (AA1) or (AA3).

[0200] The photoacid generator of the present invention may be selected from one or more members of the group consisting of: a photoacid generator composed of a cation represented by formula (AC1) and an anion represented by formula (AA1); a photoacid generator composed of a cation represented by formula (AC1) and an anion represented by formula (AA2); a photoacid generator composed of a cation represented by formula (AC1) and an anion represented by formula (AA3); a photoacid generator composed of a cation represented by formula (AC2) and an anion represented by formula (AA1); a photoacid generator composed of a cation represented by formula (AC2) and an anion represented by formula (AA3); a photoacid generator composed of a cation represented by formula (AC2) and an anion represented by formula (AA1); a photoacid generator composed of a cation represented by formula (AC2) and an anion represented by formula (AA3); a photoacid generator composed of a cation represented by formula (AC2) and an anion represented by formula (AA3); a photoacid generator composed of a cation represented by formula (AC2) and an anion represented by formula (AA3); a photoacid generator composed of a cation represented by formula (AC3) and an anion represented by formula (AA1 ... A photoacid generator composed of ions and anions represented by formula (AA2); a photoacid generator composed of cations represented by formula (AC2) and anions represented by formula (AA3); a photoacid generator composed of cations represented by formula (AC3) and anions represented by formula (AA1); a photoacid generator composed of cations represented by formula (AC3) and anions represented by formula (AA2); a photoacid generator composed of cations represented by formula (AC3) and anions represented by formula (AA3); and a photoacid generator represented by formula (AD).

[0201] Based on 100 parts by weight of the polymer, the content of the photoacid generating agent is preferably in the range of 1 to 10 parts by weight, more preferably 2 to 7 parts by weight, and very preferably 2.5 to 5 parts by weight.

[0202] The weight-average molecular weight of the photoacid generating agent is preferably 30 to 1,000, more preferably 100 to 800, very preferably 150 to 600, and most preferably 200 to 500.

[0203] polymer

[0204] These compounds contain a polymer. The polymer comprises at least one of the following repeating units (A-1) to (A-4):

[0205]

[0206] Where R 11 R 21 R 41 and R 45 Each independently is C 1-10 Alkyl groups, preferably containing C 1-10 Alkyl groups have linear, branched, or cyclic structures, and more preferably contain C. 1-6 Alkyl groups have linear, branched, or cyclic structures, with linear or branched C groups being highly preferred. 1-6 alkyl.

[0207] R 11 R 21 R 41 and R 45 One or more non-adjacent CH2 groups may optionally be replaced by -O-.

[0208] R 12 R 13 R 14 R 22 R 23 R 24 R 31 R 32 R 33 R 34 R 42 R 43 and R 44 Each independently represents H and C. 1-5 Alkyl, C 1-5 Alkyl group or -COOH, preferably H, containing C 1-5 Alkyl groups have linear, branched, or cyclic structures, more preferably H, and contain C. 1-5 The linear, branched, or cyclic structure of alkoxy or -COOH is preferred, with H or tert-butyl being highly preferred.

[0209] p11 is 0 to 4, preferably 0 to 2, and more preferably 0.

[0210] p15 is 0 to 2, preferably 1.

[0211] The condition p11+p15≤5 is satisfied.

[0212] p21 is 0 to 4, preferably 0 to 2, and more preferably 0.

[0213] p41 is 0 to 4, preferably 0 to 2, and more preferably 0.

[0214] p45 is 1 to 2, preferably 1.

[0215] The condition p41+p45≤5 is satisfied.

[0216] Exemplary examples of equation (A-1) include the following:

[0217]

[0218] Exemplary examples of equation (A-2) include the following:

[0219]

[0220] Exemplary examples of equation (A-3) include the following:

[0221]

[0222] Exemplary examples of equation (A-4) include the following:

[0223]

[0224] The polymer may contain multiple repeating units represented by formulas (A-1), (A-2), (A-3), or (A-4). For example, the polymer may contain one repeating unit (A-1) with p15=1 and another repeating unit (A-1) with p15=2, in a 1:1 ratio. In this case, the overall p15=1.5.

[0225] These structural units are appropriately mixed according to their intended use. A preferred embodiment is to mix the structural units such that the rate of increase in solubility in alkaline aqueous solutions via acid becomes appropriate.

[0226] The number n of repeating units in polymer (A) represented by formulas (A-1), (A-2), (A-3), and (A-4). A-1 n A-2 n A-3 and n A-4 The description is as follows.

[0227] n A-1 / (n A-1 +n A-2 +n A-3 +n A-4 The content is preferably 40% to 80%; more preferably 45% to 75%; very preferably 50% to 70%; and most preferably 55% to 65%.

[0228] n A-2 / (n A-1 +n A-2 +n A-3 +n A-4 The preferred concentration is 0 to 40%; more preferably 0 to 35%; very preferably 5 to 35%; and most preferably 15 to 25%.

[0229] n A-3 / (n A-1 +n A-2 +n A-3 +n A-4 The preferred concentration is 0 to 40%; more preferably 10 to 40%; very preferably 15 to 30%; and most preferably 15 to 25%.

[0230] n A-4 / (n A-1 +n A-2 +n A-3 +n A-4 The preferred concentration is 0 to 40%; more preferably 10 to 40%; very preferably 15 to 30%; and most preferably 15 to 25%.

[0231] As one embodiment of the present invention, when n A-3 When n > 0, n A-4 =0.

[0232] The polymer may be selected from one or more polymers containing at least one repeating unit (A-1) to (A-4).

[0233] In addition to the repeating units represented by formulas (A-1), (A-2), (A-3) and (A-4), the polymer may also contain one or more other repeating units.

[0234] The total number of all repeating units n contained in the polymer total The following conditions must be met:

[0235] (n A-1 +n A-2 +n A-3 +n A-4 ) / n total The content is preferably 80% to 100%, more preferably 90% to 100%, and very preferably 95% to 100%. A preferred embodiment is that the polymer does not contain other repeating units ((n...). A-1 +n A-2 +n A-3 +n A-4 ) / n total =100%).

[0236] Exemplary examples of this polymer include the following:

[0237]

[0238] Based on the content of compounds other than solvents, the content of the polymer is preferably in the range of 40 to 99% by weight, more preferably 60 to 98% by weight, very preferably 70 to 97% by weight, and most preferably 80 to 96% by weight.

[0239] The weight-average molecular weight (hereinafter referred to as Mw in some cases) of the polymer is preferably in the range of 2,000 to 50,000; more preferably 4,000 to 40,000; very preferably 6,000 to 30,000; and most preferably 8,000 to 20,000.

[0240] In this invention, Mw can be determined by gel permeation chromatography (GPC). A preferred example of this determination is using a GPC column at 40°C, with tetrahydrofuran as the elution solvent at a flow rate of 0.6 mL / min, and monodisperse polystyrene as the standard.

[0241] The plurality of compounds may include one or more additional polymers that do not contain repeating units represented by formulas (A-1), (A-2), (A-3), and (A-4). Based on the content of the compounds other than the solvent, the content of the additional polymer is preferably in the range of 0 to 10% by mass, more preferably 0 to 5% by mass, very preferably 0 to 1% by mass, and most preferably 0% by mass (excluding).

[0242] Compound B

[0243] These compounds may contain compound B. Compound B is represented by formula (II):

[0244] (II)

[0245] Where R 1 and R 5 Each independently is C 1-20 Alkyl or C 1-20 Alkoxy groups, preferably containing C 1-20 Alkyl or containing C 1-20 The alkoxy group has a linear, branched, or cyclic structure, more preferably a linear or branched C-type structure. 1-10 Alkyl groups, with branched C groups being highly preferred. 1-5 alkyl.

[0246] R 2 To R 4 Each independently represents H and C. 1-20 Alkyl or C 1-20 Alkoxy group, preferably H, containing C 1-20 Alkyl or containing C 1-20 The alkoxy group has a linear, branched, or cyclic structure, preferably H or a linear or branched C. 1-10 Alkyl groups, preferably H or linear C 1-5 Alkyl group, preferably H or methyl.

[0247] When R 1 To R 5 When each is an alkyl group independently, one or more non-adjacent CH2 groups may be optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CR=CR-, or -C≡C-.

[0248] R 3 and R 4 They can form monocyclic or polycyclic organic ring systems with each other.

[0249] Preferably, R 1 R 3 and R 5 At least one of them contains C 1-20 Alkyl groups have linear, branched, or cyclic structures; more preferably, R1 R 3 and R 5 At least one of them contains C 1-10 Alkyl groups have linear or branched structures; most preferably, R 1 R 3 and R 5 For containing C 1-5 Linear or branched structure of alkyl groups.

[0250] Preferably, R 2 and R 4 At least one of them is H, more preferably, R 2 and R 4 All are H.

[0251] Not bound by theory, but it is believed that compound B inhibits the decomposition of photoacid generators by capturing free radicals that trigger decomposition.

[0252] The molar ratio of compound B to the photoacid generating agent is in the range of 0.01 to 3, preferably 0.03 to 1.5, and more preferably 0.05 to 0.5.

[0253] Not bound by theory, but it is believed that when the molar ratio of compound B to the photoacid generator is within the above range, compound B can further and sufficiently inhibit the decomposition of the photoacid generator.

[0254] The molecular weight of compound B is preferably in the range of 10 to 1,000, more preferably 30 to 800, very preferably 50 to 500, and most preferably 100 to 300.

[0255] Based on 100 parts by weight of the polymer, the content of compound B is preferably from 0.05 to 5 parts by weight, more preferably from 0.1 to 3 parts by weight, and most preferably from 0.2 to 1.5 parts by weight.

[0256] Exemplary examples of this polymer include the following.

[0257]

[0258] solvent

[0259] These compounds may contain solvents.

[0260] The solvent may be selected from one or more members of the group consisting of: methanol, ethanol, n-propanol, isopropanol (IPA), n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethylheptanol-4, n-decanol, sec-undecanol, trimethylnonanol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol. 3,3,5-Trimethylcyclohexanol, benzyl alcohol, benzyl alcohol, diacetone alcohol, cresol, ethylene glycol, propylene glycol, 1,3-butanediol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptaethylenediol-2,4, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycerol Alcohols, Propylene Glycol Monomethyl Ether (PGME), Propylene Glycol Monomethyl Ether Acetate (PGMEA), Propylene Glycol Monoethyl Ether, Propylene Glycol Monopropyl Ether, Propylene Glycol Monobutyl Ether, Dipropylene Glycol Monomethyl Ether, Dipropylene Glycol Monoethyl Ether, Dipropylene Glycol Monopropyl Ether, Dipropylene Glycol Monobutyl Ether, Tripropylene Glycol Monomethyl Ether, 4-Methyl-2-pentanol, 3-Methyl-2-pentanol, 2-Methyl-2-pentanol, 3-Methyl-2-butanol, 2-Methyl-2-butanol, 4-Methyl-2-hexanol, 5-Methyl-2-hexanol, 3-Methyl-2-hexanol, 2-Methyl-2-hexanol, Ethyl Lactate (E L), propyl lactate, n-butyl lactate, n-pentyl lactate, butyric acid, methyl 2-hydroxyisobutyrate, methyl 2-hydroxybutyrate, methyl 3-hydroxybutyrate, methyl 4-hydroxybutyrate, ethyl 2-hydroxyisobutyrate, ethyl 2-hydroxybutyrate, ethyl 3-hydroxybutyrate, and ethyl 4-hydroxybutyrate, preferably selected from one or more members of the group consisting of: isopropanol, PGME, PGMEA, EL, propylene glycol dimethyl ether, and N-methylpyrrolidone, more preferably selected from one or more members of the group consisting of: PGME, PGMEA, and EL.

[0261] The solvent preferably has a boiling point of 30 to 300°C at 101,325 Pa, more preferably 40 to 250°C, and very preferably 50 to 200°C.

[0262] Based on 100 parts by weight of the polymer, the solvent content is preferably in the range of 500 to 3,000 parts by weight, more preferably 1,000 to 2,000 parts by weight, and most preferably 700 to 1,700 parts by weight.

[0263] Photoalkali generating agent

[0264] These compounds may contain a photoalkali generating agent. The photoalkali generating agent may be selected from one or more members of the group consisting of: 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidine n-butyltriphenylborate, nitrobenzyl-terminated 1,8-diazabicyclo[5.4.0]undec-7-ene, benzyl-terminated 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene salt of 2-(9-oxaanth-2-yl)propionic acid, 1,5,7-triazabicyclo[4.4.0]dec-5-ene-HBPh4, and triphenylmethanol, preferably triphenylmethanol.

[0265] Based on 100 parts by weight of the polymer, the content of the photoalkali generating agent is preferably 0.1 to 5 parts by weight, more preferably 0.3 to 3 parts by weight, and very preferably 0.5 to 2 parts by weight.

[0266] surfactants

[0267] These compounds may contain surfactants. The surfactants may be nonionic surfactants, anionic surfactants, or amphoteric surfactants.

[0268] Nonionic surfactants may be selected from one or more members of the group consisting of: polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene oil ether, and polyoxyethylene cetyl ether; polyoxyethylene fatty acid diesters; polyoxyethylene fatty acid monoesters; polyoxyethylene polyoxypropylene block polymers; alkynyl alcohols; alkynyl glycols; polyoxyethylene ethers of alkynyl alcohols; alkynyl glycol derivatives, such as polyoxyethylene ethers of alkynyl glycols; fluorinated surfactants, such as FLUORAD (trade name, 3M Japan); MEGAFACE (trade name: DIC); SURFLON (trade name, AGC); organosiloxane surfactants, such as KF-53 (trade name, Shin-Etsu Chemical); polyether-modified siloxanes and BYK-333 (trade name, BYK). Examples of ynylene diols include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyyn-3,6-diol, 2,4,7,9-tetramethyl-5-decyn-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 2,5-dimethyl-3-hexyn-2,5-diol, and 2,5-dimethyl-2,5-hexanediol.

[0269] In a preferred embodiment, the surfactant is a polyether-modified siloxane.

[0270] Based on 100 parts by weight of the polymer, the content of the surfactant is in the range of 0.01 to 0.5 parts by weight, more preferably 0.02 to 0.3 parts by weight, and most preferably 0.03 to 0.1 parts by weight.

[0271] Other compounds

[0272] These compounds may contain other compounds besides those mentioned above.

[0273] The other compound may be selected from one or more members of the group consisting of: surface smoothers, dyes, contrast enhancers, acids, free radical generators, substrate adhesion enhancers, plasticizers, and defoamers.

[0274] The dye can be an anthracene compound. In a preferred embodiment, the anthracene compound is 9-(4-hydroxybenzyl)-1-(4-hydroxyphenyl)anthracene.

[0275] Based on 100 parts by weight of the polymer, the content of the other compound is preferably in the range of 0.1 to 5 parts by weight, more preferably 0.3 to 3 parts by weight, and most preferably 0.5 to 2 parts by weight.

[0276] [Photoresist composition]

[0277] In another embodiment, the present invention also relates to a photoresist composition comprising a polymer, a photoacid generator, compound A represented by formula (I), and an amine.

[0278] The molar ratio of compound A to amine is in the range of 0.1 to 10.

[0279] Compound A

[0280] The photoresist composition contains compound A. Detailed information about this compound is described in the "Compound A" section of the "Methods for Stabilizing Photoacid Generating Agents in Photoresist Compositions" section.

[0281] amine

[0282] The photoresist composition may contain an amine. Details of the amine are described in the "Amine" section of the "Methods for Stabilizing Photoacid Generating Agents in Photoresist Compositions" section.

[0283] Photoacid generator

[0284] The photoresist composition contains a photoacid generating agent. Detailed information about this photoacid generating agent is described in the "Photoacid Generating Agent" section of the subsection "Methods for Stabilizing Photoacid Generating Agents in Photoresist Compositions".

[0285] polymer

[0286] The photoresist composition contains a polymer. Details of this polymer are described in the "Polymer" section of the "Methods for Stabilizing Photoacid Generating Agents in Photoresist Compositions" section.

[0287] Compound B

[0288] The photoresist composition may contain compound B. Details of compound B are described in the "Compound B" section of the "Methods for Stabilizing Photoacid Generating Agents in Photoresist Compositions" section.

[0289] solvent

[0290] The photoresist composition may contain a solvent. Details of the solvent are described in the "Solvent" section of the "Methods for Stabilizing Photoacid Generating Agents in Photoresist Compositions" section.

[0291] Photoalkali generating agent

[0292] The photoresist composition may contain a photoalkali generating agent. Detailed information about this photoalkali generating agent is described in the "Photoalkali Generating Agent" section of the "Methods for Stabilizing Photoalkali Generating Agents in Photoresist Compositions" section.

[0293] surfactants

[0294] The photoresist composition may contain a surfactant. Details of the surfactant are described in the "Surfactants" section of the "Methods for Stabilizing Photoacid Generating Agents in Photoresist Compositions" section.

[0295] Other compounds

[0296] The photoresist composition may contain other compounds besides those described above. Details of these other compounds are described in the "Other Compounds" section of the "Methods for Stabilizing Photoacid Generating Agents in Photoresist Compositions" section.

[0297] [Uses of Compound A]

[0298] In another embodiment, the invention also relates to the use of compound A for stabilizing photoacid-generating agents in photoresist compositions. Detailed information about compound A is described in the "Compound A" section of the "Methods for Stabilizing Photoacid-Generating Agents in Photoresist Compositions" section.

[0299] [Example]

[0300] The present invention will now be described with reference to several embodiments. The embodiments of the present invention are not limited to these embodiments. The mass fractions of each component in the embodiments are calculated based on 100 parts by mass of polymer.

[0301] Preparation of photoresist composition

[0302] Example 1

[0303] 0.29 parts by weight of 2-hydroxybenzoic acid and 0.371 parts by weight of tri-n-octylamine were added to 159.60 parts by weight of PGME. The PGME solutions of 2-hydroxybenzoic acid and tri-n-octylamine were mixed. 792.98 parts by weight of PGMEA and 319.52 parts by weight of EL were added to the mixed solution. 30.0 parts by weight of polymer (1) and 70.0 parts by weight of polymer (2) were added to the mixed solution. 2.0 parts by weight of bis(4-methylbenzenesulfonyl)diazomethane, 0.6 parts by weight of di(4-tert-butyl)phenyliodonium-2-(trifluoromethyl)benzenesulfonate, 1.5 parts by weight of [4-(1,1-dimethylethyl)phenyl]diphenylsulfonium perfluorobutane sulfonate, and 0.232 parts by weight of triphenylsulfonium-2-hydroxybenzoate were added to the mixed solution as photoacid generating agents. Add 0.812 parts by mass of triphenylmethanol to the mixed solution. Simultaneously add 0.06 parts by mass of polyether-modified polysiloxane and 0.84 parts by mass of 9-(4-hydroxybenzoyl)-1-(4-hydroxyphenyl)anthracene to the mixed solution.

[0304] The mixed solution was stirred overnight at 25°C, and then filtered through a 0.05µm thick filter membrane to obtain the photoresist composition.

[0305] Example 2

[0306] Except that the amount of 2-hydroxybenzoic acid was changed from 0.29 parts by weight to 0.1451 parts by weight, the preparation method of the photoresist composition was the same as that described in Example 1.

[0307] Example 3

[0308] Except that the amount of 2-hydroxybenzoic acid is changed from 0.29 parts by weight to 0.0725 parts by weight, the preparation method of the photoresist composition is the same as that described in Example 1.

[0309] Example 4

[0310] Except for the addition of 0.4398 parts by weight of 2,6-di-tert-butyl-4-methylphenol together with polyether-modified polysiloxane and 9-(4-hydroxybenzoyl)-1-(4-hydroxyphenyl)anthracene, the preparation method of the photoresist composition is the same as that described in Example 1.

[0311] Example 5

[0312] Except for the addition of 0.2199 parts by weight of 2,6-di-tert-butyl-4-methylphenol together with polyether-modified polysiloxane and 9-(4-hydroxybenzoyl)-1-(4-hydroxyphenyl)anthracene, the preparation method of the photoresist composition is the same as that described in Example 1.

[0313] Comparative Example 1

[0314] Except for the absence of 2-hydroxybenzoic acid, the preparation method of the photoresist composition is the same as that described in Example 1.

[0315] The structures of the polymers and photoacid generators used in the examples and comparative examples are as follows:

[0316] Polymer (1)

[0317]

[0318] Mw: 12,000, PDI: 1.84

[0319] Polymer (2)

[0320]

[0321] Mw: 13,000, PDL: 1.92

[0322] bis(4-methylphenylsulfonyl)diazomethane

[0323]

[0324] Di(4-tert-butyl)phenyliodonium 2-(trifluoromethyl)benzenesulfonate

[0325]

[0326] [4-(1,1-Dimethylethyl)phenyl]diphenylsulfonate perfluorobutane sulfonate

[0327]

[0328] Triphenylsulfonate 2-hydroxybenzoate

[0329]

[0330] The molar ratios of compound A to amine and compound B to photoacid generating agent are shown in Table 1.

[0331] [Table 1]

[0332]

[0333]

[0334] Aging test

[0335] The photoresist compositions of Examples 1 to 5 and Comparative Example 1 were each divided into two portions and stored in brown glass bottles. One portion was placed at -20°C as a reference sample. The other portion was placed at 40°C for accelerated aging testing for one week to simulate the aging effect of half a year at room temperature.

[0336] coating

[0337] The aged photoresist composition was coated onto 8-inch wafers using an MK-8 clean track (Tokyo Electron). First, the wafers were placed in a 90°C oven for hexamethyldisilazane (HMDS) pretreatment for 35 seconds. The spin-coating speed was adjusted to approximately 1200 rpm to obtain a film thickness of 310 nm. Subsequently, the wafers coated with the photoresist composition underwent a post-coat bake (PAB) process at 90°C for 35 seconds. A 43 nm thick top anti-reflective coating (TARC AZ Aquatar-VIII A30) was then applied onto the photoresist layer at approximately 780 rpm.

[0338] Photolithography

[0339] The wafer was ready for photolithography. The photolithography process used a KrF FPS300-EX5 stepper lithography machine (Canon). This stepper lithography machine has a numerical aperture of 0.63 and a σ value of 0.65. A 180nm CD photomask manufactured by IT&DT was selected for photolithography. With the mask size fixed as described above, multiple resist patterns were formed by varying the exposure and performing the subsequent development process. A calibration curve was plotted based on the exposure data. According to this calibration curve, the exposure amount at which the measured size of the resist pattern coincided with the mask size (a pattern with a linewidth and spacing of 1:1) was determined. The determined exposure amount is denoted as Eop. The Eop value of the reference sample stored at -20°C is denoted as Eop1, while the Eop value of the aged sample maintained at 40°C is denoted as Eop2.

[0340] development

[0341] After photolithography, the wafer is sent back to the clean track for further development. The wafer undergoes exposure-after-baking (PEB) at 135°C for 90 seconds. Then, it is developed for 30 seconds using a 2.38 wt% tetramethylammonium hydroxide developer to form a resist pattern on the wafer.

[0342] Stability assessment

[0343] The rate of change between Eop1 and Eop2 is calculated according to the following formula.

[0344] ΔEop=(Eop1-Eop2) / Eop1×100 (%)

[0345] The stability of photoacid generators is evaluated according to the following criteria.

[0346] A: ΔEop < 9%

[0347] B: 9% ≤ ΔEop < 15%

[0348] C: ΔEop≥15%

[0349] The evaluation results are shown in Table 2.

[0350] [Table 2]

[0351]

[0352] As shown in Table 2, the ΔEop values ​​of Examples 1 to 5 are improved compared to the ΔEop value of Comparative Example 1.

Claims

1. A method for stabilizing a photoacid-generating agent in a photoresist composition, comprising step (a): (a) A mixture of multiple compounds to form a photoresist composition, wherein the multiple compounds comprise a polymer, a photoacid generator, an amine and compound A represented by formula (I); (I) Where R 1 To R 5 Each independently represents H and C. 1-20 Alkyl, C 1-20 Alkoxy, OH or NH2, preferably H or C 1-10 Alkyl or OH, more preferably H or OH; When R 1 To R 5 When each is an alkyl group independently, one or more non-adjacent CH2 groups may be optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CR=CR-, or -C≡C-.

2. The method according to claim 1, wherein the molar ratio of compound A to amine is in the range of 0.1 to 10, preferably 0.2 to 8, more preferably 0.3 to 5, and most preferably 0.5 to 3. Preferably, based on 100 parts by weight of the polymer, the amine content is in the range of 0.1 to 1 part by weight, more preferably 0.2 to 0.9 parts by weight, and most preferably 0.3 to 0.8 parts by weight.

3. The method according to claim 1 or 2, wherein the plurality of compounds further comprises compound B represented by formula (II): (II) Where R 1 and R 5 Each independently is C 1-20 Alkyl or C 1-20 Alkoxy, preferably C 1-20 Alkyl, more preferably C 1-10 alkyl; Where R 2 To R 4 Each independently represents H and C. 1-20 Alkyl or C 1-20 Alkoxy group, preferably H or C 1-20 Alkyl, more preferably H or C 1-10 alkyl; When R 1 To R 5 When each is an alkyl group independently, one or more non-adjacent CH2 groups may be optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CR=CR- or -C≡C-; Where R 3 and R 4 They can form monocyclic or polycyclic organic ring systems with each other.

4. The method according to claim 3, wherein the molar ratio of compound B to the photoacid generating agent is in the range of 0.01 to 3, preferably 0.03 to 1.5, more preferably 0.05 to 0.

5.

5. The method according to any one of claims 1 to 4, wherein the amine is a tertiary amine, preferably selected from one or more members of the group consisting of: trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, tri-n-heptamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine and tri-dodecanamine, more preferably selected from one or more members of the group consisting of: tri-n-heptamine, tri-n-octylamine and tri-n-nonylamine.

6. The method according to any one of claims 1 to 5, wherein, Photoacid generators include cations represented by formula (AC1): (AC1) Where R 1 and R 2 Each independently is C 1-20 Alkyl, C 1-20 Aryl or C 1-20 Aryl alkyl group, preferably C 1-15 Aryl or C 1-15 Aryl alkyl group, more preferably C 1-10 Aryl.

7. The method according to any one of claims 1 to 6, wherein the plurality of compounds further comprises a solvent, preferably selected from one or more members of the group consisting of: isopropanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, ethyl lactate and N-methylpyrrolidone; more preferably selected from one or more members of the group consisting of: propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and ethyl lactate.

8. A photoresist composition comprising a polymer, a photoacid generating agent, compound A represented by formula (I), and an amine. The molar ratio of compound A to amine is in the range of 0.1 to 10, preferably 0.2 to 8, more preferably 0.3 to 5, and most preferably 0.5 to 3. Preferably, based on 100 parts by weight of the polymer, the amine content is in the range of 0.1 to 1 part by weight, more preferably 0.2 to 0.9 parts by weight, and most preferably 0.3 to 0.8 parts by weight; (I) Where R 1 To R 5 Each independently represents H and C. 1-20 Alkyl, C 1-20 Alkoxy, OH or NH2, preferably H or C 1-10 Alkyl or OH, more preferably H or OH; When R 1 To R 5 When each is an alkyl group independently, one or more non-adjacent CH2 groups may be optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CR=CR-, or -C≡C-.

9. The photoresist composition according to claim 8, wherein the composition further comprises compound B represented by formula (II): (II) Where R 1 and R 5 Each independently is C 1-20 Alkyl or C 1-20 Alkoxy, preferably C 1-20 Alkyl, more preferably C 1-10 alkyl; R 2 To R 4 Each independently represents H and C. 1-20 Alkyl or C 1-20 Alkoxy group, preferably H or C 1-20 Alkyl, more preferably H or C 1-10 alkyl; When R 1 To R 5 When each is an alkyl group independently, one or more non-adjacent CH2 groups may be optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CR=CR- or -C≡C-; Where R 3 and R 4 They can form monocyclic or polycyclic organic ring systems with each other.

10. The photoresist composition according to claim 9, wherein the molar ratio of compound B to photoacid generator is in the range of 0.01 to 3, preferably 0.03 to 1.5, more preferably 0.05 to 0.

5.

11. The photoresist composition according to any one of claims 8 to 10, wherein the amine is a tertiary amine, preferably selected from one or more members of the group consisting of: trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, tri-n-heptylamine, tri-n-nonylamine, tri-n-decylamine and tri-dodecanamine, more preferably selected from one or more members of the group consisting of: tri-n-heptylamine, tri-n-octylamine and tri-n-nonylamine.

12. The photoresist composition according to any one of claims 8 to 11, wherein the photoacid generator comprises a cation represented by formula (AC1); (AC1) Where R 1 To R 2 Each independently is C 1-20 Alkyl, C 1-20 Aryl or C 1-20 Aryl alkyl group, preferably C 1-15 Aryl or C 1-15 Aryl alkyl group, more preferably C 1-10 Aryl.

13. The photoresist composition according to any one of claims 8 to 12, wherein the plurality of compounds further comprises a solvent, preferably selected from one or more members of the group consisting of: isopropanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, ethyl lactate and N-methylpyrrolidone, more preferably selected from one or more members of the group consisting of: propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and ethyl lactate.

14. The photoresist composition according to any one of claims 8 to 13, wherein the polymer comprises at least one of the following repeating units (A-1) to (A-4): Where R 11 R 21 R 41 and R 45 Each independently is C 1-10 alkyl; R 11 R 21 R 41 and R 45 One or more non-adjacent CH2 groups may be replaced by -O-; R 12 R 13 R 14 R 22 R 23 R 24 R 31 R 32 R 33 R 34 R 42 R 43 and R 44 Each independently represents H and C. 1-5 Alkyl, C 1-5 Alkyl groups or -COOH; p11 is 0 to 4, p15 is 0 to 2, and p11+p15≤5; p21 is 0 to 4; n21 is between 0 and 1; p41 is 0 to 4, p45 is 1 to 2, and p41 + p45 ≤ 5.

15. The use of compound A, represented by formula (I), for stabilizing photoacid-generating agents in photoresist compositions: (I) Where R 1 To R 5 Each independently represents H and C. 1-20 Alkyl, C 1-20 Alkoxy, OH or NH2, preferably H or C 1-10 Alkyl or OH, more preferably H or OH; When R 1 To R 5 When each is an alkyl group independently, one or more non-adjacent CH2 groups may be optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CR=CR-, or -C≡C-.

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