A thermal acid generator, a coating composition, and a pattern forming method.

Abstract

Provided are a thermal acid generator, a coating composition, and a patterning method. 【Solution means】A thermal acid generator compound containing an anion and a nitrogen-containing cation, wherein the anion is a compound represented by formula (1): (In formula (1), ring A 1 is a monocyclic C 3~60 aromatic group, a polycyclic C 3~60 aromatic group, a C 3~15 monocyclic aliphatic group, or a C 3~15 polycyclic aliphatic group, and each L 1 is independently a single bond or one or more linking groups, L 1 does not contain fluorine, and each of the remaining groups is as defined herein). TIFF2026137058000031.tif60166

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority and benefits of U.S. Provisional Patent Application No. 63 / 758,678, filed with the U.S. Patent and Trademark Office on 14 February 2025, which is incorporated herein by reference in its entirety.

[0002] The present invention relates to a thermal acid generator, a coating composition, and a pattern forming method using such a coating composition. The present invention finds particular applicability to lithography applications in the semiconductor manufacturing industry. [Background technology]

[0003] Photoresist underlayer compositions are used in the semiconductor industry as etching masks for lithography in the latest technology nodes for integrated circuit manufacturing. These compositions are commonly used in 3- and 4-layer photoresist integration schemes, where layers of an anti-reflective coating containing organic or silicon and a patternable photoresist film are placed on top of a high-carbon-content bottom layer.

[0004] When chemically amplified photoresist compositions for ArF or extreme ultraviolet (EUV) lithography are prepared using resins that may contain by-products, the number of defects (surface defects) in the developed resist pattern can be a problem, even if properties such as sensitivity, resolution, and resist pattern shape are satisfactory. These surface defects include problems such as scum and bridging between resist patterns.

[0005] EUV lithography is a cutting-edge technology poised to replace photolithography for mass production of semiconductors in shapes of several nanometers. Currently, EUV lithography has become the preferred patterning technique over the 193nm immersion process for high-volume production of product nodes smaller than 10nm. In EUV lithography, fewer photons are present in the exposure area than in ArF lithography. Due to the lack of photons and the reduced pitch of the pattern, the effects of shot noise are more pronounced with respect to the pattern profile. Bridging defects between scum and resist patterns, such as nano-bridging defects in line-to-space patterns with a 3×nm pitch, can lead to fatal bridging defects after overall pattern transfer by the etching process.

[0006] Therefore, there is still a need for new photoresist underlayer materials that can reduce delamination losses in photoresists for ArF and EUV lithography and / or reduce scum and bridging defects. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] U.S. Patent Application Publication No. 2011 / 0033801A1 [Patent Document 2] U.S. Patent Application Publication No. 2019 / 0129305A1 [Non-patent literature]

[0008] [Non-Patent Document 1] Zeno W. Wicks, Jr., Frank N. Jones, S. Peter Pappas, “Organic Coatings, Science and Technology,” pp246-257 (John Wiley&Sons, 1999, second edition) [Non-Patent Document 2] Houben-Weyl, “Methoden der Organischen Chemie, Band E20, Makromolekulare Soffe, Polyester,” pp1405 - 1429. (Georg Thieme Verlag, Stuttgart 1987) [Non-Patent Document 3] McCutcheon’s Emulsifiers and Detergents, North American Edition for the Year 2000 [Summary of the Invention] [Means for Solving the Problems]

[0009] One aspect relates to a thermal acid generator compound containing an anion and a nitrogen-containing cation, wherein the anion is represented by formula (1): [Chemical Formula] (In formula (1), ring A 2 , 1~20 , 1 , 2a , 3~15 , , 2a , 3~60 , , 1 , 1 , 1 , 3~15 , 1~20 , 3~60 , 2a , 1 , , 2a , , 1 , is a monocyclic C 3~60 aromatic group, a polycyclic C 3~60 aromatic group, a C 3~15 monocyclic aliphatic group, or a C 3~15 polycyclic aliphatic group, each L 1 is independently a single bond or one or more linking groups, L 1 does not contain fluorine, each L 2 is independently a single bond or one or more divalent linking groups, P is a polymerizable group, each R 1 is independently a monovalent non-hydrogen substituent; each R 1 may optionally further contain one or more divalent linking groups as part of its structure, each X 1 is independently -O-, -S-, -N(R 2a )-, -C(O)-, -S(O)R 2a -, or -S(O2)R 2a -, and R 2a is independently substituted or unsubstituted C 1~20 alkyl, substituted or unsubstituted C 1~20Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 Selected from heteroaryls, each Z 1 It independently contains an anion stabilizing group and at least one Z 1 It is configured to form an intramolecular non-covalent bond with a sulfonic acid anion group to form a ring having 5 to 9 ring atoms, or a ring having 5 to 8 ring atoms, Z 1 These are independently -OH, -C(O)OH, -SH, -C(O)SH, and -NHS(O)2R 3 -S(O)2R 3 ,-S(O)R 3 -S(O)2NHS(O)2R 3 -CH (=NOH), or -B (R 4 ) Selected from 2, each Z 1 It may optionally further include one or more divalent linking groups as part of its structure, and each R 3 These are independently trifluoromethyl, hydroxyl, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 Selected from heteroaryls, each R 4 These are, independently, hydrogen, fluorine, hydroxyl, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 Selected from heteroaryls, two R 1 They come together and arbitrarily Cy 1 They may form a fused ring, and the fused ring may optionally further contain one or more divalent linking groups as part of its structure, and one Z 1 and one R 1 Together, arbitrarily Cy 1They may form a fused ring, and the fused ring may optionally contain one or more divalent linking groups as part of its structure, provided that each a and b is an integer between 0 and 2 independently, but the sum of a and b is 1 or more, c is an integer between 0 and 10, d is an integer between 1 and 3, e is 0 or 1, and n is an integer between 0 and 4).

[0010] Another embodiment relates to a coating composition comprising a thermal acid generator, a polymer, and a solvent.

[0011] Another embodiment relates to a pattern forming method comprising: applying a layer of the coating composition described in claim 10 onto a substrate to obtain a lower layer composition; curing the lower layer composition to form a lower layer film; applying a layer of the photoresist composition onto the lower layer film to obtain a photoresist composition layer; pattern-like exposure of the photoresist composition layer with activating radiation to obtain an exposed photoresist composition layer; and developing the exposed photoresist composition layer to obtain a resist relief image. [Modes for carrying out the invention]

[0012] Here, exemplary embodiments are referenced in detail, and examples thereof are illustrated in this description. In this regard, exemplary embodiments may take different forms and should not be construed as being limited to the descriptions expressed herein. Accordingly, exemplary embodiments are described below only for the purpose of illustrating aspects of this description. As used herein, the terms “and / or” encompass any combination of one or more of the related enumerated items. Expressions such as “at least one of” qualify the entire list of elements, but not the individual elements of the list, when preceding a list of elements.

[0013] As used herein, the terms “a,” “an,” and “the” do not imply a limitation of quantity and should be interpreted as encompassing both singular and plural forms unless otherwise specifically stated herein or clearly contradicted by the context. “Or” means “and / or” unless otherwise specified. The modifying phrase “about” used in relation to quantity includes the expressed value and has meaning determined by the context (e.g., the degree of error associated with the measurement of a particular quantity). All scopes disclosed herein include endpoints, which are independently combinable with one another. The suffix “(s)” includes both singular and plural forms of the term it modifies and is intended to include at least one of those terms. “Optional” or “optionally” means that the event or situation described thereafter may or may not occur, and that the description includes both the cases in which the event occurs and the cases in which the event does not occur. The terms “first,” “second,” etc., used herein do not imply order, quantity, or importance, but rather are used to distinguish one element from another. When an element is said to be “on” another element, it may be in direct contact with the other element, or an intervening element may exist between them. In contrast, when an element is said to be “directly on” another element, no intervening element is present. It should be understood that the components, elements, limitations, and / or features described in the embodiments may be combined in any preferred manner in various embodiments.

[0014] Unless otherwise specified, all terms used herein (including technical and scientific terms) have the same meaning as those generally understood by those skilled in the art to which the invention pertains. Terms such as those defined in commonly used dictionaries should be interpreted as having the same meaning as those defined in the relevant art and in relation to this disclosure, and it will be further understood that unless explicitly defined herein, they should not be interpreted in an ideal or overly formal sense.

[0015] As used herein, "chemical beam" or "radiation" means, for example, the emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet (EUV) light, X-rays, electron beams, and particle beams such as ion beams. Furthermore, in this invention, "light" means chemical beam or radiation. A krypton fluoride laser (KrF laser) is a specific type of excimer laser that may be called an exciplex laser. "Excimer" is an abbreviation for "excitation dimer," while "exciplex" is an abbreviation for "excitation complex." An excimer laser uses a mixture of a noble gas (argon, krypton, or xenon) and a halogen gas (fluorine or chlorine) and emits coherent stimulating radiation (laser light) in the ultraviolet range under suitable conditions of electrical stimulation and high pressure. Furthermore, unless otherwise specified, "exposure" in this specification includes not only exposure using far ultraviolet light such as mercury lamps and excimer lasers, X-rays, and extreme ultraviolet (EUV) light, but also writing using particle beams such as electron beams and ion beams.

[0016] As used herein, the terms “hydrocarbon” means an organic compound having at least one carbon atom and at least one hydrogen atom; “alkyl” means a linear or branched saturated hydrocarbon group having the specified number of carbon atoms and a valency of 1; “alkylene” means an alkyl group having a valency of 2; “hydroxyalkyl” means an alkyl group substituted with at least one hydroxyl group (-OH); “alkoxy” means “alkyl-O-”; “carboxyl” and “carbone” "Acid group" refers to a group having the formula "-C(=O)-OH"; "cycloalkyl" refers to a monovalent group having one or more saturated rings in which all ring members are carbon; "cycloalkylene" refers to a cycloalkyl group having a valency of 2; "alkenyl" refers to a monovalent hydrocarbon group having at least one carbon-carbon double bond, either straight-chain or branched-chain; "alkenoxy" refers to "alkenyl-O-"; "alkenylene" refers to an alkenyl group having a valency of 2; "cycloalkenyl" refers to a group having at least one carbon- "A" refers to a non-aromatic cyclic divalent hydrocarbon group having at least three carbon atoms and a carbon double bond; "Alkynyl" refers to a monovalent hydrocarbon group having at least one carbon-carbon triple bond; the term "aromatic group" refers to a monocyclic or polycyclic aromatic ring system that satisfies Huckel's rule (4n + 2π electrons) and contains carbon atoms in the ring; the term "heteroaromatic group" refers to an aromatic group that contains one or more heteroatoms (e.g., 1 to 4 heteroatoms) selected from N, O, and S instead of carbon atoms in the ring; "A" "Riel" refers to a monovalent monocyclic or polycyclic aromatic ring system in which all ring members are carbon, and may include a group having an aromatic ring fused to at least one cycloalkyl or heterocycloalkyl ring; "Arylene" refers to an aryl group having a valence of 2; "Alkylaryl" refers to an aryl group substituted with an alkyl group; "Arylalkyl" refers to an alkyl group substituted with an aryl group; "Aryloxy" refers to "aryl-O-"; and "Arylthio" refers to "aryl-S-".

[0017] The prefix "hetero" means that a compound or group contains at least one ring member that is a heteroatom (e.g., 1, 2, 3, or 4 or more heteroatoms) instead of a carbon atom, and each heteroatom can be independently N, O, S, Si, or P. "Heteroatom-containing group" refers to a substituent containing at least one heteroatom, "heteroalkyl" refers to an alkyl group having at least one heteroatom instead of carbon, and "heterocycloalkyl" refers to a cycloalkyl group having 1 to 4 heteroatoms as ring members instead of carbon. The terms "heterocycloalkylene" refers to a heterocycloalkyl group having a valence of 2, and "heteroaryl" refers to an aromatic 4-8 member monocyclic, 8-12 member bicyclic, or 11-14 member tricyclic group having 1-4 heteroatoms (in the case of a monocyclic), 1-6 heteroatoms (in the case of a bicyclic), or 1-9 heteroatoms (in the case of a tricyclic) (for example, in the case of a monocyclic, bicyclic, or tricyclic, respectively, carbon atoms and 1-3, 1-6, or 1-9 heteroatoms of N, O, or S). Examples of heteroaryl groups include pyridyl, furyl (furyl or furanyl), imidazolyl, benzimidazolyl, pyrimidinyl, thiophenyl or thienyl, quinolinyl, indolyl, thiazolyl, etc., and "heteroarylene" refers to a heteroaryl group having a valence of 2.

[0018] The term "halogen" refers to a monovalent substituent that is fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iodo). The prefix "halo" refers to a group that contains one or more fluoro, chloro, bromo, or iodo substituents instead of a hydrogen atom. A combination of halo groups (e.g., bromo and fluoro) or a fluoro group alone may exist. For example, the term "haloalkyl" refers to an alkyl group substituted with one or more halogens. As used herein, "substituted C 1~8 "Haloalkyl" refers to C substituted with at least one halogen. 1~8This refers to an alkyl group that is further substituted with one or more other substituents that are not halogens. It should be understood that because halogen atoms do not replace carbon atoms, substitution of a group at a halogen atom is not considered a heteroatom-containing group.

[0019] Each of the aforementioned substituents may be optionally substituted unless otherwise explicitly specified. The term “optionally substituted” means either substituted or unsubstituted. “Substituted” means that at least one hydrogen atom of the chemical structure or group is replaced by another terminal substituent, typically monovalent, provided that the valency does not exceed the normal valency of the specified atom. When the substituent is oxo (i.e., O), two geminal hydrogen atoms on the carbon atom are replaced by a terminal oxo group. It is further noted that the oxo group is bonded to the carbon atom via a double bond to form a carbonyl (C=O) group, which is represented herein as -C(O)-. Combinations of substituents or variables are permitted. Exemplary substituents that may be present in a “substituted” position include, but are not limited to, nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (O), amino (-NH2), mono or di (C) 1~6 ) Alkylamino, alkanoyl (e.g., acyl, etc.) 2~6 Alkanoyl groups), formyl (-C(O)H), carboxylic acids or their alkali metal salts or ammonium salts; esters (including acrylates, methacrylates, and lactones), for example, C 2~6 Alkyl esters (-C(O)O-alkyl or -OC(O)-alkyl) and C 7~13 Aryl esters (-C(O)O-aryl or -OC(O)-aryl); amides (-C(O)NR2 (where R is hydrogen or C) 1~6 (It is alkyl), carboxamide (-CH2C(O)NR2 (R is hydrogen or C) 1~6 Alkyl, halogen, thiol (-SH), C 1~6 Alkylthio(-S-alkyl), thiocyano(-SCN), C 1~6 Alkyl, C 2~6 Alkenil, C 2~6 Alkinyl, C1~6 Haloalkyl, C 1~9 Alkoxy, C 1~6 Haloalkoxy, C 3~12 Cycloalkyl, C 5~18 Cycloalkenyl, C 2~18 Heterocycloalkenyl, a C having at least one aromatic ring 6~12 Aryl (e.g., phenyl, biphenyl, naphthyl, etc., where each ring is substituted or unsubstituted aromatic), C having 1 to 3 independent or fused rings and 6 to 18 ring carbon atoms. 7~19 Arylalkyls, arylalkoxys having 1-3 independent or fused rings and 6-18 ring carbon atoms, C 7~12 Alkylaryl, C 3~12 Heterocycloalkyl, C 3~12 Heteroaryl, C 1~6 Alkylsulfonyl (-S(O)2-alkyl), C 6~12 Examples include arylsulfonyl (-S(O)2-aryl) or tosyl (CH3C6H4SO2-).

[0020] In this specification, unless otherwise defined, "divalent linking group" refers to -O-, -S-, -Te-, -Se-, -C(O)-, -C(O)O-, -N(R ’ )-, C(O)N(R ’ )-, -S(O)-, -S(O)2-, -C(S)-, -C(Te)-, -C(Se)-, substitution or non-substitution C 1~30 Alkylene, substituted, or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 This refers to a divalent group containing one or more heteroarylenes or combinations thereof, where each R ’ These are, independently, hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30It is heteroaryl. Typically, the divalent linking group is -O-, -S-, -C(O)-, -C(O)O-, -N(R’)-, C(O)N(R ’ )-, -S(O)-, -S(O)2-, substituted or unsubstituted C 1~30 alkylene, substituted or unsubstituted C 3~30 cycloalkylene, substituted or unsubstituted C 3~30 heterocycloalkylene, substituted or unsubstituted C 6~30 arylene, substituted or unsubstituted C 3~30 heteroarylene, or one or more of combinations thereof, and R’ is hydrogen, substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C1-20 heteroalkyl, substituted or unsubstituted C6-30 aryl, or substituted or unsubstituted C 3~30 heteroaryl. More typically, the divalent linking group is -O-, -S-, -C(O)-, -C(O)O-, -N(R ’ )-, -C(O)N(R’)-, substituted or unsubstituted C 1~10 alkylene, substituted or unsubstituted C 3~10 cycloalkylene, substituted or unsubstituted C 3~10 heterocycloalkylene, substituted or unsubstituted C 6~10 arylene, substituted or unsubstituted C 3~10 heteroarylene or at least one of combinations thereof, and R is hydrogen, substituted or unsubstituted C 1~10 alkyl, substituted or unsubstituted C 1~10 heteroalkyl, substituted or unsubstituted C 6~10 aryl or substituted or unsubstituted C 3~10 heteroaryl.

[0021] As used herein, “acid-unstable group” refers to a group whose bonds are optionally and typically cleaved by the action of an acid during heat treatment, resulting in the formation of a polar group such as a carboxylic acid group or an alcohol group. In some cases, the acid-unstable group may be formed on a polymer, and optionally and typically, the portion bound to the cleaved bond is detached from the polymer. In other systems, the nonpolymer compound may contain an acid-unstable group that can be cleaved by the action of an acid, resulting in the formation of a polar group such as a carboxylic acid group or an alcohol group on the cleaved portion of the nonpolymer compound. Such acids are typically photo-generated acids in which bond cleavage occurs during post-exposure baking (PEB). However, embodiments are not limited thereto, and for example, such acids may be thermally generated. Preferred acid-unstable groups include, for example, tertiary alkyl ester groups, secondary or tertiary ester groups having an aryl group, secondary or tertiary ester groups having a combination of an alkyl group and an aryl group, tertiary alkoxy groups, acetal groups, or ketal groups. In this technical field, acid-unstable groups are generally referred to as "acid-cleavable groups," "acid-cleavable protecting groups," "acid-unstable protecting groups," "acid-leaving groups," "acid-degradable groups," and "acid-sensitive groups."

[0022] The inventors have discovered a thermoacid generator (TAG) comprising an anionic core comprising (i) an anionic group and (ii) a cyclic group substituted with an anion-stabilizing group configured to stabilize the anionic group by intramolecular non-covalent bonding. In other words, the anion-stabilizing group is configured to form intramolecular non-covalent bonds with the anionic group. For example, although not bound by theory, the anion-stabilizing group can form intramolecular non-covalent bonds with the anionic group, or for example, the anion-stabilizing group can form intramolecular non-covalent bonds with the anionic group. In some embodiments, intramolecular non-covalent bonds can be formed in situ, such as when the thermoacid generator compound is included in a photoresist underlayer coating composition.

[0023] A thermoacid generator compound comprising an anion and a nitrogen-containing cation is provided, wherein the anion is represented by formula (1): [ka]

[0024] In equation (1), ring A 1 This is a single ring C 3~60 Aromatic group, polycyclic C 3~60 Aromatic group, C 3~15 Monocyclic aliphatic group, or C 3~15 It is a polycyclic aliphatic group. For example, in some embodiments, ring A 1 This is a single ring C 3~60 Aromatic group or polycyclic carbon 3~60 It may be an aromatic group. In another embodiment, ring A 1 C 3~15 Monocyclic aliphatic group or C 3~15 It may also be a polycyclic aliphatic group. Ring A 1 X as described in this specification 1 It optionally contains heteroatoms represented as follows.

[0025] In some embodiments, ring A 1 This is a single ring C 3~60 Aromatic group or polycyclic carbon 6~60 It may be an aromatic group. The term "aromatic group" includes both aromatic and heteroaromatic groups. In one embodiment, a monocyclic C 3~60 Aromatic groups are monocyclic C 3~60 Arylene group or monocyclic C 3~60 Heteroarylene groups, typically monocyclic C 6~30 Arylene group, or monocyclic carbon 3~30 It may be a heteroarylene group. 3~60 When an aromatic group is polycyclic, it should be understood that the number of carbon atoms in that group is sufficient to make the group chemically feasible. For example, "polycyclic C 3~60 Aromatic group is a polycyclic carbon group. 10~60 Arylene group or polycyclic carbon 10~30 This may refer to an allerene group. Exemplary monocyclic or polycyclic C 3~60Examples of aromatic groups, though not limited to them, include benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylene, chrysene, phenalene, benzo[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene.

[0026] In some embodiments, ring A 1 C 3~15 Monocyclic aliphatic group or C 3~15 It may also be a polycyclic aliphatic group. For example, ring A 1 C 3~15 Monocyclic aliphatic group or C 6~15 It may also be a polycyclic aliphatic group. In the structure of formula 1, X 1 It should be understood that the ring A may optionally contain heteroatom groups represented as such. For example, ring A 1 This is a single ring C 3~15 Cycloalkylene, monocyclic C 3~15 Cycloalkylene, monocyclic C 3~15 Heterocycloalkylene, monocyclic C 3~15 Heterocycloalkylene, polycyclic C 6~15 Cycloalkylene, polycyclic C 6~15 Cycloalkylene, polycyclic C 6~15 Heterocycloalkylene, or polycyclic C 6~15 It may also be a heterocycloalkylene. Ring A 1 Examples of alicyclic groups include, but are not limited to, cyclopentane, cyclohexane, decalin, tetrahydrofuran, thiolane, thian, thian-1,1-dioxide, thian-1-oxide, tetrahydropyran, adamantyl, bicyclo[3.2.1]octane, bicyclo[4.3.0]nonane, and bicyclo[3.3.1]nonane.

[0027] In equation (1), each L 1 Independently, L is a single bond or one or more linking groups. 1 It does not contain fluorine. In other words, L 1 If L is one or more linking groups, 1It does not contain fluorine. Each of the one or more divalent linking groups may be substituted or unsubstituted. Exemplary divalent linking groups are -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~30 Alkylene, substituted, or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarylenes, or combinations thereof, can be selected independently, R ’ C is hydrogen, substituted or unsubstituted. 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It may be a heteroaryl compound. Typically, L 1 C is a single bond, or a substituted or unsubstituted C. 1~20 Alkylene, preferably single-bonded or substituted or unsubstituted C 1~10 It can be a cycloalkylene.

[0028] If b is 0, L 1 L may be a single bond or one or more divalent linking groups. 1 It should be understood that it does not contain fluorine.

[0029] In equation (1), each L 2 These are, independently, single bonds or one or more divalent linking groups. Each of the one or more divalent linking groups may be substituted or unsubstituted. Exemplary divalent linking groups are, independently, -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, and -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~30 Alkylene, substituted, or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 You can choose from heteroarylenes or combinations thereof, R ’ C is hydrogen, substituted or unsubstituted. 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It may be a heteroaryl. In some embodiments, L 2 is -O-, -N(R ’ )-,-C(O)N(R ’ )-, -S(O)-, -S(O)2-, substitution or non-substitution C 1~30 Alkylene, substituted, or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 It comprises one or more divalent linking groups selected from heteroarylenes or combinations thereof, R ’ These are, independently, hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It is a heteroaryl compound.

[0030] In formula (1), P is a polymerizable group. Examples of polymerizable groups include, but are not limited to, (meth)acrylate groups, vinyl groups, vinyl aromatic groups, vinyl ether groups, vinyl ketone groups, vinyl ester groups, epoxy groups, etc., or combinations thereof.

[0031] In equation (1), each R 1 Each R is independently a monovalent nonhydrogen substituent; 1 It may optionally further include one or more divalent linking groups as part of its structure. For example, each R 1These are, independently, halogen, hydroxyl, substituted or unsubstituted C 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Cycloalkenes, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 6~30 Aryloxy, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Alkyl heteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 They may also be heteroaryloxys. Typically, each R 1 These are independently hydroxyl, substituted, or unsubstituted C 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Cycloalkenes, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 6~30 Aryloxy, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Alkyl heteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 Heteroaryloxy may also be acceptable.

[0032] In equation (1), each R 1It may further include one or more divalent linking groups as part of its structure. Each of the one or more divalent linking groups may be substituted or unsubstituted. Exemplary divalent linking groups are -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~30 Alkylene, substituted, or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 You can choose from heteroarylenes or combinations thereof, R ’ C is hydrogen, substituted or unsubstituted. 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It may be a heteroaryl compound.

[0033] In some embodiments, one or more R 1 Each of these may independently further include an acid-unstable group, a lactone-containing group, a base-solubilizing group, or a combination thereof.

[0034] In some embodiments, one or more R 1 Each of these may independently contain polymerizable sites as all or part of its structure. For example, R 1 The structure may further include, in whole or in part, (meth)acrylate groups, vinyl aromatic groups, vinyl ether groups, vinyl ketone groups, and / or vinyl ester groups.

[0035] In equation (1), each X 1 These are independently -O-, -S-, and -N(R 2a )-, -C(O)-, -S(O)R 2a -, or -S(O2)R 2a - and R 2a These are independently substituted or unsubstituted C1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 Selected from heteroaryls. If n is 0, then X 1 is ring A 1 It should be understood that it does not exist inside.

[0036] In equation (1), each Z 1 It independently contains an anion stabilizing group and at least one Z 1 It is configured to form an intramolecular non-covalent bond with a sulfonic acid anion group to form a ring having 5 to 9 ring atoms, or a ring having 5 to 8 ring atoms, Z 1 These are independently -OH, -C(O)OH, -SH, -C(O)SH, and -NHS(O)2R 3 -S(O)2R 3 ,-S(O)R 3 -S(O)2NHS(O)2R 3 -CH (=NOH), or -B (R 4 ) Selected from 2; each Z 1 It may optionally further include one or more divalent linking groups as part of its structure. Typically, each anion stabilizing group Z 1 This can be independently selected from -OH, C(O)OH, SH, or -B(OH)2, preferably at least one anionic stabilizing group Z 1 It contains -OH.

[0037] In equation (1), each R 3 These are independently trifluoromethyl, hydroxyl, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 Selected from heteroaryls.

[0038] In equation (1), each R 4 These are, independently, hydrogen, fluorine, hydroxyl, substituted or unsubstituted C1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 Selected from heteroaryls.

[0039] For example, each Z 1 It may be configured to form an intramolecular non-covalent bond with a sulfonic acid anion group to form a ring having 5 to 9 ring atoms, or 5 to 8 ring atoms, or typically 6 or 7 ring atoms. Ring A 1 two or more anionic stabilizing groups Z 1 If it contains at least one anionic stabilizing group Z 1 It should be understood that it is configured to form an intramolecular non-covalent bond with at least one sulfonic acid anion group to form a ring having 5 to 9 ring atoms, or a ring having 5 to 8 ring atoms. Similarly, L 1 two or more anionic stabilizing groups Z 1 If it contains at least one anionic stabilizing group Z 1 It is configured to form an intramolecular non-covalent bond with at least one sulfonic acid anion group to form a ring having 5 to 9 ring atoms, or a ring having 5 to 8 ring atoms.

[0040] In this specification, “anion stabilizing group” refers to any suitable group that can stabilize an anionic group via an intramolecular non-covalent bond, as defined herein. Therefore, anion stabilizing groups are configured to form an intramolecular non-covalent bond with an anionic group. In other words, anion stabilizing groups can form an intramolecular non-covalent bond with an anionic group. In this specification, “non-covalent bond” can refer to any non-covalent interaction between anion stabilizing group and an anionic group. As described above, non-covalent interactions are intramolecular interactions, and the anion stabilizing group and the anionic group reside on the same molecule. Examples of non-covalent bonds include hydrogen bonds or ionic bonds. Anion stabilizing groups may include protic groups. For example, the intramolecular non-covalent bond may be an intramolecular hydrogen bond between a suitable hydrogen atom of the anion stabilizing group and the anionic group. For example, in some embodiments, anion stabilizing groups may be configured to form an intramolecular hydrogen bond with an anionic group; for example, in some embodiments, anion stabilizing groups may form an intramolecular hydrogen bond with an anionic group. In some embodiments, intramolecular non-covalent bonds include dipole-dipole interactions, ion-dipole interactions, or combinations thereof. In this specification, “non-covalent bond” does not include bonds based solely on van der Waals forces.

[0041] In some embodiments, the anionic stabilizing group may have a pKa of 25 or less, typically 20 or less, or 18 or less, preferably 16 or less.

[0042] In equation (1), each Z 1 It may optionally further include one or more divalent linking groups as part of its structure. Each of the one or more divalent linking groups may be substituted or unsubstituted. Exemplary divalent linking groups include -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~10 Alkylene, substituted, or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 You can choose from heteroarylenes or combinations thereof, R ’ C is hydrogen, substituted or unsubstituted. 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It may be a heteroaryl compound. Typically, Z 1 -O-, -C(O)-, -C(O)O-, -SO-, -S(O)2-, -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~30 Alkylene, substituted, or unsubstituted C 3~10 Cycloalkylene, substituted or unsubstituted C 3~10 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 It may further contain one or more divalent linking groups selected from heteroarylenes or combinations thereof, R ’ C is hydrogen, substituted or unsubstituted. 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It may be a heteroaryl compound.

[0043] In equation (1), the two R 1 Together, they form ring A 1 A fused ring may be optionally formed, and the fused ring may optionally further contain one or more divalent linking groups as part of its structure. Each of the one or more divalent linking groups may be substituted or unsubstituted, and the fused ring may be substituted or unsubstituted.

[0044] In equation (1), one Z 1 and one R 1The rings may optionally combine to form a fused ring with ring A1, and the fused ring may optionally contain one or more divalent linking groups as part of its structure. Each of the one or more divalent linking groups may be substituted or unsubstituted, and the fused ring may be substituted or unsubstituted. Ring A 1 The condensed ring formed together may be aliphatic or aromatic.

[0045] In equation (1), a and b are independent integers between 0 and 2, but the sum of a and b must be 1 or greater. Typically, a is 1 or 2 and b is 0.

[0046] In equation (1), c is an integer between 0 and 10. Typically, c is an integer between 0 and 2, and preferably c is 0 or 1.

[0047] In equation (1), n ​​is an integer between 1 and 3. Typically, d is 1 or 2, preferably d is 1. For example, in some embodiments, a may be 1 or 2 and d may be 1. In some embodiments, d may be 1 and L 1 It is a single bond. L 1 It should be understood that if it is a single bond, then b is 0.

[0048] In equation (1), e is either 0 or 1. Typically, e is 0.

[0049] In equation (1), n ​​is an integer between 0 and 4. Typically, n is 0 or 1. Preferably, n is 0.

[0050] In some embodiments, anions can be represented by equation (1a): [ka] (In the formula, ring A 1 , X 1 , R 1 , Z 1 , L 1 , L 2P, a, c, d, e, and n are as defined for equation (1), respectively.

[0051] In some embodiments, the anion can be represented by formula (1b): [ka] (In the formula, ring A 1 , X 1 , R 1 , Z 1 , L 1 , L 2 (P, b, c, d, e, and n are as defined for equation (1), respectively.)

[0052] Examples of anions represented by formula (1) include the following: [ka] [ka] [ka] [ka] [ka] [ka]

[0053] Other exemplary anions of formula (1) include the following: [ka]

[0054] Other exemplary anions of formula (1) include the following: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0055] In some embodiments, the conjugate acid of the thermoacid generator compound may have a pKa of 0 or less. Typically, the conjugate acid of the thermoacid generator compound may have a pKa of -2 or less, preferably -5 or less. The conjugate acid of the thermoacid generator compound may have a pKa of, for example, -15 to 0 or -15 to -2.

[0056] In some embodiments, the anion may not contain a trifluoromethyl group and a difluoromethylene group. In other words, in some embodiments, the anion of formula (1) may not contain a trifluoromethyl group and a difluoromethylene group. For example, in some embodiments, the anion may not contain fluorine (the anion of formula (1) may not contain fluorine).

[0057] The anions of the thermal acid generating compound can be obtained from commercially available sources or may be prepared by any suitable method. For example, such anions can be prepared as described in the examples of this specification.

[0058] The thermal acid generator of formula (1) further comprises nitrogen-containing cations. Exemplary cations include ammonium species and pyridinium species, which may be optionally substituted with acid-unstable groups, lactone-containing groups, base-solubilizing groups, polymerizable groups, or combinations thereof. Exemplary polymerizable groups include, but are not limited to, (meth)acrylate groups, epoxy groups, vinyl aromatic groups, vinyl ether groups, vinyl ketone groups, and / or vinyl ester groups.

[0059] In some embodiments, the nitrogen-containing cation may be of formula (2) or (3): [ka]

[0060] In equation (2), each R 10 R is independently a hydrogen or non-hydrogen substituent. 10 It may further include one or more divalent linking groups as part of its structure. For example, each R 10 These are, independently, hydrogen, deuterium, halogen, hydroxyl, substituted or unsubstituted C 1~30 Alkyl, substituted, or unsubstituted C 2~30 Alkenyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Cycloalkenes, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 6~30 Aryloxy, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Alkyl heteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 They may also be heteroaryloxys. Typically, each R 10These are independently hydroxyl, halogen, substituted or unsubstituted C 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Cycloalkenes, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 6~30 Aryloxy, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Alkyl heteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 Heteroaryloxy may also be acceptable.

[0061] In equation (2), each R 10 It may optionally further include one or more divalent linking groups as part of its structure. Each of the one or more divalent linking groups may be substituted or unsubstituted. Exemplary divalent linking groups include -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~30 Alkylene, substituted, or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 You can choose from heteroarylenes or combinations thereof, R ’ C is hydrogen, substituted or unsubstituted. 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It may be a heteroaryl compound.

[0062] In some embodiments, one or more R 10 Each of these may independently contain an acid-unstable group, a lactone-containing group, a base-solubilizing group, a polymerizable group, or a combination thereof.

[0063] In equation (2), p is an integer between 0 and 5. Typically, p is 1 or 2.

[0064] In equation (3), R 11 ~R 14 Each of these is independently a hydrogen or non-hydrogen substituent, and R 11 ~R 14 Each of these may independently further contain one or more divalent linking groups as part of its structure. Typically, R 11 ~R 14 At least one of them is neither hydrogen nor deuterium. For example, R 11 ~R 14 These are, independently, hydrogen, deuterium, and substituted or unsubstituted C. 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Cycloalkenes, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Alkyl heteroaryl, or substituted or unsubstituted C 4~30 It may also be a heteroarylalkyl. Typically, R 11 ~R 14 These are, independently, hydrogen, deuterium, and substituted or unsubstituted C. 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Cycloalkenes, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Alkyl heteroaryl, or substituted or unsubstituted C 4~30 Heteroarylalkyl groups may also be used.

[0065] In some embodiments, R 11 ~R 14 One or more of these may independently further include an acid-unstable group, a lactone-containing group, a base-solubilizing group, a polymerizable group, or a combination thereof.

[0066] In equation (3), R 11 ~R 14 Each of them is either independent or connected to another group R via a single bond or divalent linking group. 11 ~R 14 They may be connected to form a ring.

[0067] In some embodiments, nitrogen-containing cations can be selected from the following: [ka]

[0068] Cationic compounds for heat-generating agents can be obtained from commercial suppliers or prepared using common synthetic methods.

[0069] Suitable thermoacid generator compounds include those obtained from any combination of the anions and cations mentioned above. Thermoacid generator compounds can be prepared by combining anionic and cationic species under appropriate conditions.

[0070] Furthermore, a coating composition comprising a thermal acid generator, a polymer, and a solvent is also provided.

[0071] The thermal acid generator may be present in the coating composition in an amount of 0.1 to 99% by weight (wt%), more typically 1 to 80%, 1 to 75%, or 1 to 60%, based on the total solids content of the coating composition. In some embodiments, the coating composition may contain two or more different thermal acid generator compounds described herein.

[0072] The coating composition comprises a polymer, preferably a polymer containing crosslinkable groups. Any suitable polymer that can be used to form an underlayer coating composition for a photoresist can be used. In some embodiments, the coating composition comprises a polymer containing cyanurate structural units derived from a compound of formula (4), for example: [ka]

[0073] In formula (4), K, L, and M are each independently linear or branched carbon atoms, each of which may be optionally substituted with a carboxylic acid group. 1~10 hydrocarbon group, C 1~10 Alkoxycarbonyl group, C 1~10 Alkanoyloxy group, or C 1~5 Alkoxycarbonyl group or C 1~5 Linear or branched carbon atoms may be optionally substituted with substituted alkoxy groups. 1~10 It is a hydroxyalkyl group.

[0074] In equation (4), for K, L, and M, C 1~10 hydrocarbon group, C 1~10 Alkoxycarbonyl group, C 1~10 Alkanoyloxy group, and C 1~10 Each of the hydroxyalkyl groups is a halogen, amino group, thiol group, epoxy group, amide group, C 1~5 Alkyl alkyl group, C 3~8 Cycloalkyl groups, C 3~20 Heterocycloalkyl groups, C 2~5 Alkenyl group, C 1~5 Alkoxy group, C 2~5Alkenoxy group, C 6~12 Aryl group, C 6~12 Aryloxy group, C 7~13 Alkylaryl group, or C 7~13 It may be optionally substituted with at least one alkylaryloxy group. 3~8 Cycloalkyl groups and C 3~20 The heterocycloalkyl group may optionally be substituted with an oxo group (=O) on at least one ring carbon atom. At least one hydrogen atom of the polymer derived from the monomer of formula (4) may be substituted with a functional group independently selected from hydroxyl, carboxyl, thiol, amino, epoxy, alkoxy, amide, vinyl, and combinations thereof. Of these, hydroxyl, carboxyl, or alkoxy are preferred.

[0075] Polymers can be formed by conventional polycondensation techniques, such as those described in (Non-Patent Document 1) and its references, or (Non-Patent Document 2) and its references. In one embodiment, a diol or polyol and a dicarboxylic acid or polycarboxylic acid are placed in a conventional polymerization vessel and reacted at about 150-280°C for several hours. Optionally, an esterification catalyst may be used to reduce the reaction time. It is also understood that esterifiable derivatives of polycarboxylic acids, such as dimethyl esters or anhydrides of polycarboxylic acids, can be used to prepare polyesters. Exemplary polyols and polycarboxylic acids include isocyanurate polyols and isocyanurate polycarboxylic acids. Polyester polymers can be linear or branched. Examples of polymers containing cyanurate structural units are also shown in (Patent Document 1) and (Patent Document 2), the contents of which are incorporated herein by reference in their entirety.

[0076] Suitable dicarboxylic acids or polycarboxylic acids, or their corresponding alkyl esters, that can be used to form a second polymer include saturated and unsaturated dicarboxylic acids, such as isophthalic acid, maleic acid, maleic anhydride, malonic acid, fumaric acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, 2-methyl-1,6-hexanoic acid, pimelic acid, suberic acid, dodecanediic acid, phthalic acid, phthalic anhydride, 5-tert-butylisophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, azelaic acid, sebacic acid, tetrachlorophthalic anhydride, chlorendic acid, isophthalic acid, trimellitic anhydride, terephthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, dimeric fatty acids, or anhydrides of any of these acids, or combinations thereof.

[0077] Suitable diols and polyols include ethylene glycol, diethylene glycol, triethylene glycol and higher polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and higher polypropylene glycol, 1,3-propanediol, 1,4-butanediol and other butanediols, 1,5-pentanediol and other pentanediols, hexanediol, decanediol and dodecanediol, glycerol, trimethylolpropane, trimethylolethane, neopentyl glycol, pentaerythritol, and cyclohexyl Examples include, but are not limited to, sanidimethanol, dipentaerythritol, 1,2-methyl-1,3-propanediol, 1,4-benzyldimethanol, 2,4-dimethyl-2-ethylhexane-1,3-diol, isopropylidenebis(p-phenylene-oxypropanol-2), 4,4'-dihydroxy-2,2'-diphenylpropane, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol (or a mixture of 1,3- and 1,4-cyclohexanedimethanol, which may be cis or trans), sorbitol, etc., or combinations thereof.

[0078] The polymer may optionally contain one or more additional repeating units distinct from the repeating units comprising formula (4). These additional repeating units may include one or more additional units for the purpose of modifying the properties of the coating composition, such as etch rate and solubility. Exemplary further units may include one or more (meth)acrylates, vinyl ethers, vinyl ketones, and vinyl esters. When present in the polymer, one or more additional repeating units are typically used in amounts of 99 mol% or less, typically 3 to 80 mol%, based on the total repeating units of the polymer.

[0079] Preferably, the polymer will have a weight-average molecular weight (Mw) of 1,000 to 100,000 grams (g / mol) per molecule, more typically 2,000 to 30,000 g / mol, and a number-average molecular weight (Mn) of 500 to 1,000,000 g / mol. w Or M n ) is preferably measured by gel permeation chromatography (GPC).

[0080] The amount of polymer in the coating composition may be 15% to 99% by weight based on the total solids content of the coating composition. For example, the amount of polymer in the coating composition may be 15% to 95% by weight based on the total solids content of the coating composition, but is not limited to this.

[0081] The coating composition may further contain a crosslinking agent, which is not particularly limited and may be any crosslinkable substance that can initiate a crosslinking reaction by heat. The crosslinkable compound and polymer may harden, crosslink, or solidify when exposed to heat, as a thermal acid generator releases acid.

[0082] Any suitable crosslinking agent can be used in this composition, provided that the crosslinking agent has at least two, preferably at least three, sites that can react with the polymer under appropriate conditions such as acidic conditions. Examples of crosslinking agents include novolac resins, epoxy-containing compounds, melamine compounds, guanamine compounds, isocyanate-containing compounds, benzocyclobutene, benzoxazine, etc., typically methylol, C1- 10 Alkoxymethyl, and C2~ 10 Examples of suitable crosslinking agents include, but are not limited to, any of the aforementioned compounds having two or more substituents selected from acyloxymethyl, more generally three or more substituents. Examples of suitable crosslinking agents include: [ka]

[0083] The amount of crosslinkable compound in the coating composition may be 0% to 15% by weight based on the total solids content of the coating composition. For example, the amount of crosslinking agent in the coating composition may be 0% to 10% by weight based on the total solids content of the coating composition, or 0% to 5% by weight based on the total solids content of the coating composition, but is not limited to these amounts.

[0084] The coating composition further comprises a solvent. Preferably, the solvent is an organic solvent conventionally used in the manufacture of electronic devices. Suitable solvents include, for example, aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane and 1-chlorohexane; alcohols such as methanol, ethanol, 1-propanol, iso-propanol, tert-butanol, 2-methyl-2-butanol, 4-methyl-2-pentanol and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone) (DAA); propylene glycol monomethyl ether (PGME); ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane and anisole; acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, These solvents include ketones such as cyclohexanone (CHO); esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), hydroxyisobutyrate methyl ester (HBM), and acetate acetate; lactones such as gamma-butyrolactone (GBL) and epsilon-caprolactone; lactams such as N-methylpyrrolidone; nitriles such as acetonitrile and propionitrile; cyclic or acyclic carbonate esters such as propylene carbonate, dimethyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, and propylene carbonate; polar aprotic solvents such as dimethyl sulfoxide and dimethylformamide; water; and combinations thereof. Among these, preferred solvents include one or more of PGME, PGMEA, EL, GBL, HBM, CHO, and DAA, or combinations thereof.

[0085] The total solvent content in the composition (i.e., the cumulative solvent content of all solvents) is typically 40–99% by weight, for example, 60–99% by weight, or 85–99% by weight, based on the total weight of the coating composition. The desired solvent content will depend, for example, on the desired thickness of the coated layer and the coating conditions. Furthermore, the coating composition may further contain one or more polymers in addition to the polymers described above, but different in composition. For example, the coating composition may contain additional polymers as described above, but with different compositions.

[0086] Furthermore, or instead, one or more additional polymers may be selected from those well known in photoresist technology, such as polyacrylates, polyvinyl ethers, polyesters, polynorbornene, polyacetals, polyethylene glycols, polyamides, polyacrylamides, polyphenols, novolacs, styrene-based polymers, polyvinyl alcohols, or combinations thereof.

[0087] The coating composition may further contain one or more additional, optional additives. For example, optional additives may include chemical dyes and contrast dyes, striation inhibitors, plasticizers, rate accelerators, sensitizers, photodegradable deactivators (PDQ) (also known as photodegradable bases), basic deactivators, surfactants, or combinations thereof. If present, optional additives are typically present in the composition in an amount of 0.01 to 10% by weight based on the total solids content of the composition.

[0088] The coating composition may optionally contain one or more surface leveling agents (or surfactants). Typical surfactants include those exhibiting amphiphilic properties. This means that they may be both hydrophilic and hydrophobic at the same time. Amphiphilic surfactants have a hydrophilic head group with a strong affinity for water and a long, hydrophobic tail that is organic and repels water. Suitable surfactants may be ionic (i.e., anionic, cationic) or nonionic. Further examples of surfactants include silicone surfactants, poly(alkylene oxide) surfactants, and fluorochemical surfactants. Suitable nonionic surfactants include, but are not limited to, octyl and nonylphenol ethoxylates such as TRITON X-114, X-100, X-45, and X-15, and branched secondary alcohol ethoxylates such as TERGITOL TMN-6 (Dow Chemical Company, Midland, Michigan, USA) and PF-656 (Omnova Solutions, Beachwood, Ohio, USA). Further exemplary surfactants include alcohol (primary and secondary) ethoxylates, amine ethoxylates, glucosides, glucamine, polyethylene glycol, poly(ethylene glycol-co-propylene glycol), or other surfactants disclosed in Non-Patent Literature 3, published by Manufacturers Confectioners Publishing Co. of Glen Rock, NJ. Nonionic surfactants that are acetylenediol derivatives may also be suitable. Such surfactants are commercially available from Air Products and Chemicals, Inc. (Allentown, PA) and are sold under the trade names SURFYNOL and DYNOL. Additional suitable surfactants include other polymer compounds such as the triblock EO-PO-EO copolymers PLURONIC 25R2, L121, L123, L31, L81, L101, and P123 (BASF, Inc.).When used, such surfactants may be present in the coating composition in small amounts, for example, more than 0% by weight and up to 1% by weight, based on the total solids content of the coating composition.

[0089] Another embodiment provides a coated substrate comprising a cured layer of a coating composition disposed on a substrate; and a photoresist layer disposed on the layer of the coating composition. As used herein, the term “cured layer” refers to a layer derived from a coating composition after the composition has been disposed on a substrate and subsequently cured to form a coating layer or film. In other words, curing of a coating composition forms a cured layer derived from the coating composition.

[0090] A further aspect of the present invention provides a method for forming a pattern. This method includes: applying a layer of the coating composition of the present invention onto a substrate; curing the layer of the coating composition to form a base layer; applying a layer of the photoresist composition onto the base layer to form a photoresist layer; pattern-like exposure of the photoresist layer with activating radiation; and developing the exposed photoresist layer to obtain a resist relief image.

[0091] A wide variety of substrates can be used in pattern formation methods, with electronic device substrates being typical. Suitable substrates include, for example, packaging substrates such as multi-chip modules; flat panel display substrates; integrated circuit substrates; substrates for light-emitting diodes (LEDs) such as organic light-emitting diodes (OLEDs); semiconductor wafers; and polycrystalline silicon substrates. Suitable substrates can be in the form of wafers, such as those used in the manufacture of integrated circuits, optical sensors, flat panel displays, optical integrated circuits, and LEDs. As used herein, the term “semiconductor wafer” is intended to encompass “electronic device substrates,” “semiconductor substrates,” “semiconductor devices,” and various packages for various levels of interconnection, such as single-chip wafers, multiple-chip wafers, packages for various levels, or other assemblies requiring solder connections. Such substrates may be of any suitable size. Typical wafer substrate diameters are 200 mm to 300 mm, but wafers with smaller and larger diameters may be suitably used according to the present invention. As used herein, the term “semiconductor substrate” includes any substrate having one or more semiconductor layers or structures that may optionally contain the effective or operational parts of a semiconductor device. A semiconductor device means a semiconductor substrate on which at least one microelectronic device is batch-manufactured or in the process of being manufactured.

[0092] The substrate is typically composed of one or more of the following materials: silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. The substrate may include one or more layers and patterned features. The layers may include one or more conductive layers such as aluminum, copper, molybdenum, tantalum, titanium, tungsten, alloys of such metals, nitrides or silicides, doped amorphous silicon, or doped polysilicon layers; one or more dielectric layers such as silicon oxide, silicon nitride, silicon oxynitride, or metal oxide layers; semiconductor layers such as single-crystal silicon; and combinations thereof. The layers can be formed by various techniques, such as chemical vapor deposition (CVD) such as plasma-enhanced CVD (PECVD), low-pressure CVD (LPCVD), or epitaxial growth; physical vapor deposition (PVD) such as sputtering or evaporation; or electroplating.

[0093] In a particular pattern formation method of the present invention, it may be desirable to apply one or more lithography layers, such as a hard mask layer, for example, a spin-on-carbon (SOC), amorphous carbon, or metal hard mask layer; a CVD layer such as a silicon nitride (SiN) layer, a silicon oxide (SiO) layer, or a silicon oxynitride (SiON) layer; an organic or inorganic BARC layer; or a combination thereof, onto the upper surface of the substrate before forming the photoresist underlayer (coating layer) of the present invention. Such layers, together with the topcoat underlayer and photoresist layer of the present invention, form a lithography material stack. Typical lithography stacks that may be used in the pattern formation method of the present invention include, for example, the following: SOC layer / underlayer / photoresist layer; SOC layer / SiON layer / underlayer / photoresist layer; SOC layer / SiARC layer / underlayer / photoresist layer; SOC layer / metal hard mask layer / underlayer / photoresist layer; amorphous carbon layer / underlayer / photoresist layer; and amorphous carbon layer / SiON layer / underlayer / photoresist layer.

[0094] The coating composition can be coated onto a substrate by any suitable means, such as spin coating, slot die coating, doctor bladeding, curtain coating, roller coating, spray coating, immersion coating, etc. In the case of semiconductor wafers, spin coating is preferred. In a typical spin coating method, the coating composition is applied to a substrate that is rotating at a speed of 500 to 4000 rpm for a period of 15 to 90 seconds to obtain the desired layer of the coating composition on the substrate. It will be well understood by those skilled in the art that the thickness of the coating composition can be adjusted by changing the spin speed and the solid content of the coating composition. The underlayer formed from the coating composition typically has a dry layer thickness of 1 to 50 nm, more typically 1 to 20 nm.

[0095] The applied coating composition may optionally be soft-baked at a relatively low temperature to remove any solvents and other relatively volatile components from the coating composition. Typically, the coated substrate is baked at a temperature of 150°C or less, preferably 60–130°C, more preferably 90–120°C. The baking time is typically 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes, more preferably 6–120 seconds. If the substrate is a wafer, such a baking step may be performed by heating the wafer on a hot plate. The soft-baking step may be performed as part of the curing of the applied coating composition, or it may be omitted entirely.

[0096] The applied coating composition is then cured to form a photoresist underlayer. The applied photoresist underlayer composition should be cured sufficiently so that the resulting underlayer does not mix with, or mixes minimally with, any subsequently applied layers, such as photoresists or other organic or inorganic layers directly placed on top of the photoresist underlayer. The applied photoresist underlayer composition may be cured in an oxygen-containing atmosphere such as air, or in an inert atmosphere such as nitrogen, under conditions such as heating sufficient to provide a cured coating layer. This curing process is preferably carried out on a hot plate type apparatus, but oven curing may be used to obtain equivalent results. The curing temperature should be sufficient for the TAG to cure the layer throughout. For example, it should be sufficient for a thermal acid generator to release acid, and for the released acid to cause crosslinking. Typically, curing is carried out at a temperature of 150°C or higher, preferably 150 to 450°C. The curing temperature is more preferably 180°C or higher, more preferably 200°C or higher, and even more preferably 200 to 400°C. The curing time is typically 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes, more preferably 45 seconds to 2 minutes, and even more preferably 45 to 90 seconds. Optionally, a gradient or multi-stage curing process may be used. A gradient bake typically begins at a relatively low (e.g., ambient) temperature, and the temperature is raised at a constant or variable gradient rate to a higher target temperature. A multi-stage curing process involves curing in two or more temperature planes, typically a first stage at a lower bake temperature and one or more additional stages at higher temperatures. Conditions for such gradient or multi-stage curing processes are known to those skilled in the art and may allow for the omission of a prior soft bake process.

[0097] After the applied photoresist underlayer composition has cured and the underlayer film has been formed, one or more processing layers, such as a photoresist layer, a hard mask layer such as a metal hard mask layer, or an organic or inorganic BARC layer, may be placed on the cured photoresist underlayer film. The photoresist layer can be formed directly on the surface of the photoresist underlayer, or it can be formed on the photoresist underlayer on one or more intervening layers. In this case, one or more intervening processing layers, such as those described above, can be formed sequentially on the entire surface of the photoresist underlayer, and then the photoresist layer can be formed. Determining appropriate layers, thicknesses, and coating methods is well known to those skilled in the art.

[0098] A wide variety of photoresists can be suitably used in the method of the present invention, and are typically positive-toned materials. Suitable photoresists include, for example, materials in the EPIC series of photoresists available from DuPont Electronics & Imaging (Marlborough, Massachusetts). The photoresist can be applied to the substrate by known coating techniques such as those described above in relation to the photoresist underlayer composition, and spin coating is typical. A typical thickness for the photoresist layer is 10 to 300 nm. The photoresist layer is typically then soft-baked to minimize the solvent content in the layer, thereby forming a non-stick coating and improving the adhesion of the layer to the substrate. Soft baking can be done on a hot plate or in an oven, with a hot plate being typical. A typical soft bake is performed at a temperature of 70 to 150°C and for a time of 30 to 90 seconds.

[0099] The photoresist layer is then exposed to activating radiation through a photomask to create a difference in solubility between exposed and unexposed areas. The reference herein to exposing a photoresist composition to activating radiation indicates that the radiation can form a latent image in the photoresist composition. The photomask has optically transparent and optically opaque regions, corresponding to the regions of the resist layer exposed and unexposed by the activating radiation, respectively. The exposure wavelength is typically less than 400 nm, more commonly less than 300 nm, e.g., 248 nm (KrF), 193 nm (ArF), or EUV wavelength (e.g., 13.5 nm), or an electron beam. In a preferred embodiment, the exposure wavelength is 193 nm or EUV wavelength. The exposure energy is typically 10–150 mJ / cm², depending, for example, the exposure tool and the components of the photosensitive composition. 2 That is the case.

[0100] Following the exposure of the photoresist layer, a post-exposure bake (PEB) is typically performed. PEB can be performed, for example, on a hot plate or in an oven. PEB is typically carried out at a temperature of 70–150°C and for 30–90 seconds. This forms a latent image defined by the boundary between polarity-switched and non-switched regions (corresponding to the exposed and unexposed regions, respectively). The exposed photoresist layer is then developed using a suitable developer to provide a patterned photoresist layer.

[0101] The pattern of the photoresist layer can then be transferred to one or more underlying layers, including the photoresist underlayer, and to the substrate by appropriate etching techniques, such as plasma etching using the appropriate gas species for each layer being etched. Depending on the number of layers and the materials involved, the pattern transfer may involve multiple etching steps using different etching gases. The patterned photoresist layer, photoresist underlayer, and other optional layers in the lithography stack can be removed after the pattern transfer to the substrate using conventional techniques. Optionally, one or more layers in the stack can be removed or consumed after the pattern transfer to the underlying layers and before the pattern transfer to the substrate. The substrate is then further processed according to known methods for forming electronic devices.

[0102] The concept of the present invention is further illustrated by the following examples, which are intended to be non-limiting. All compounds and reagents used herein are commercially available, unless the procedure is given below. [Examples]

[0103] Unless otherwise noted, all reactions were carried out under ambient atmospheric conditions. All chemicals were used directly from suppliers. Nuclear magnetic resonance (NMR) spectra of all compounds were obtained using a 400 MHz spectrometer unless otherwise noted. Chemical shifts are reported as δ (parts per million, ppm) values ​​relative to the internal heavy chloroform residual signal. Multiplicity is indicated by s (singlet), d (doublet), t (triplet), m (multiplet), dd (doublet of doublets), dt (doublet of triplets), tt (triplet of triplets), and br (broad singlet).

[0104] Synthesis of N-benzyl-N,N-dimethylbenzeneaminium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate (TAG-1) [ka] 10.0 g of sodium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate and 8.73 g of N-benzyl-N,N-dimethylbenzeneaminium chloride were dissolved in 50 ml of dichloromethane and 50 mL of deionized water (DI), and the mixture was stirred at room temperature for 16 hours. The organic layer was washed with 5 × 25 mL of DI water, and concentrated under reduced pressure to obtain N-benzyl-N,N-dimethylbenzeneaminium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate (14.1 g, 88%) TAG-1 as a colorless liquid. 1 H NMR(400MHz,DMSO-d6)δ 9.98(s,2H),7.85-7.81(m,2H),7.62-7.57(m,3H),7.44-7.39(m,1H),7.33-7.29(t,2H),7.04-7.01(d,2H),6.8 7(s,2H),5.02(s,2H),4.24-4.21(t,2H),3.59(s,6H),1.70-1.63(m,2H),1.44-1.35(m,2H),0.94-0.90(t,3H).

[0105] Synthesis of N-benzyl-N,N-dimethylbenzeneaminium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (TAG-2) [ka] 7.0 g of sodium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate and 6.44 g of N-benzyl-N,N-dimethylbenzeneaminium chloride were dissolved in 35 mL of dichloromethane and 35 mL of deionized water, and then stirred at room temperature for 16 hours. The organic layer was washed with DI water (5 × 17.5 mL) and concentrated under reduced pressure to obtain N-benzyl-N,N-dimethylbenzeneaminium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (10.0 g, 87%) TAG-2 as a colorless liquid. 1H NMR(400MHz,DMSO-d6)δ 10.64(s,1H),7.86-7.81(m,2H),7.63-7.57(m,4H),7.45-7.30(m,5H),7.04-7.01(d,2H),5.01( s,2H),4.27-4.24(t,2H),3.58(s,6H),1.72-1.65(m,2H),1.46-1.37(m,2H),0.95-0.91(t,3H).

[0106] Synthesis of 2,4,6-trimethylpyridine-1-ium-4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate (TAG-3) [ka] To an aqueous solution (50 mL) of sodium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate (5.0 g), 3.2 mL of 5 N hydrochloric acid aqueous solution (at 0°C) was slowly added. After stirring the reaction mixture for 30 minutes, 2,4,6-trimethylpyridine (2.04 g) was added dropwise, followed by the addition of dichloromethane (50 mL). The two-phase mixture was heated to room temperature and stirred for 16 hours. The organic layer was separated, washed with water (5 × 25 mL), precipitated in heptane (500 mL), filtered, and dried to obtain 2,4,6-trimethylpyridine-1-ium-4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate (4.3 g, 69%) TAG-3 as a white solid. 1 H NMR(400MHz,DMSO-d6)δ 14.85(br,1H),9.92(s,2H),7.56(s,2H),6.83(s,2H),4.25-4.21(t,2H),2.62 (s,6H),2.49(s,3H),1.71-1.64(m,2H),1.45-1.36(m,2H),0.95-0.91(t,3H).

[0107] Synthesis Example 4: Tripropylammonium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate (TAG-4) [ka] A 5N aqueous hydrochloric acid solution (3.2 mL) was slowly added to sodium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate (5.0 g) in water (50 mL) at 0 °C. After stirring the reaction mixture for 30 minutes, tripropylamine (2.41 g) was added dropwise, followed by the addition of dichloromethane (50 mL). The biphasic mixture was warmed to room temperature and stirred for 16 hours. The organic layer was separated, washed with water (5 × 25 mL), concentrated under reduced pressure, and dried to obtain tripropylammonium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate (6.1 g, 93%) TAG-4 as a white solid. 1 H NMR (400 MHz, DMSO-d6) δ 9.92 (s, 2H), 8.86 (br, 1H), 6.84 (s, 2H), 4.25 - 4.21 (t, 2H), 3.31 - 2.97 (m, 6H), 1.71 - 1.57 (m, 8H), 1.45 - 1.36 (m, 2H), 0.95 - 0.89 (m, 12H).

[0108] Synthesis of Polymer (P1) Tris(2-hydroxyethyl) isocyanurate (15.0 g), tris(2-carboxyethyl) isocyanurate (10.0 g), n-butanol (10.1 g), and p-toluenesulfonic acid (0.25 g) were dissolved in anisole (16.7 g). The mixture was heated at 150 °C for 3 hours under a Dean-Stark trap. Then, the mixture was cooled to room temperature and diluted with methyl 2-hydroxyisobutyrate (80 g). A portion of the resulting solution was added with p-toluenesulfonic acid (0.04 g) and 1,3,4,6-tetrakis(butoxymethyl)tetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione (8.0 g), and heated at 50 °C for 4 hours. The reaction mixture was quenched with triethylamine (0.2 mL), cooled to room temperature, precipitated with isopropanol / heptane, filtered, and dried to obtain the target polymer (12.2 g, 48.8%) P1 as a white powder.

[0109] Preparation of Coating Composition The coating composition was prepared by mixing the components in the amounts shown in Table 1. The amounts are described in grams. The abbreviations in Table 1 are as follows: A1: tetramethoxymethyl glycoluril; S1: methyl 2-hydroxyisobutyrate; S2: propylene glycol monomethyl ether acetate; S3: propylene glycol methyl ether; TAG-5: N-benzyl-N,N-dimethylbenzeneaminium trifluoromethanesulfonate.

[0110]

Table 1

[0111] Membrane strip evaluation The coating composition was spin-coated separately onto silicon wafers at 1500 rpm using a spinner, and the wafers were heated at 205 °C for 60 seconds using a hot plate to form thin films (film thickness of 200 - 300 Å). These thin films were exposed to 30 mL of a PGME / PGMEA (7:3) mixture for 90 seconds and post-baked on a hot plate at 110 °C for 60 seconds. The thicknesses of the original coated films and the exposed and post-baked films were measured, and the change in film thickness (Δstrip) (thickness of the exposed and post-baked film - thickness of the original coated film) was calculated. The results are shown in Table 3 in angstroms (Å) units.

[0112]

Table 2

[0113] This disclosure has been described in connection with what is presently considered to be practical and exemplary embodiments, but it is to be understood that the invention is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalent arrangements within the spirit and scope of the appended claims.

Claims

1. A thermoacid generator compound comprising an anion and a nitrogen-containing cation, wherein the anion is of formula (1): 【Chemistry 1】 A thermoacid generator compound represented by (In formula (1), Ring A １ This is a single ring C ３～６０ Aromatic group, polycyclic C ３～６０ aromatic group, C ３～１５ Monocyclic aliphatic group, or C ３～１５ It is a polycyclic aliphatic group, Each L １ Independently, L is a single bond or one or more linking groups. １ It does not contain fluorine. Each L ２ These are independently single bonds or one or more divalent linking groups. P is a polymerizable group, Each R １ is independently a monovalent non-hydrogen substituent, and each R １ may optionally further contain one or more divalent linking groups as part of its structure, each X １ These are independently -O-, -S-, and -N(R ２ａ )-, -C(O)-, -S(O)R ２ａ -, or -S(O ２ ) R ２ａ - and R ２ａ These are independently substituted or unsubstituted C １～２０ Alkyl, substituted, or unsubstituted C １～２０ Heteroalkyl, substituted, or unsubstituted C ６～３０ Aryl, or substituted or unsubstituted C ３～３０ Selected from heteroaryls, Each Z １ It independently contains an anion stabilizing group and at least one Z １ It is configured to form an intramolecular non-covalent bond with a sulfonic acid anion group to form a ring having 5 to 9 ring atoms, or a ring having 5 to 8 ring atoms, Z １ These are independently -OH, -C(O)OH, -SH, -C(O)SH, -NHS(O) ２ R ３ , -S(O) ２ R ３ , -S(O)R ３ , -S(O) ２ NHS (O) ２ R ３ -CH (=NOH), or -B (R ４ ) ２ Selected from, each Z １ It may optionally further include one or more divalent linking groups as part of its structure. Each R ３ These are independently trifluoromethyl, hydroxyl, substituted or unsubstituted C １～２０ Alkyl, substituted, or unsubstituted C １～２０ Heteroalkyl, substituted, or unsubstituted C ６～３０ Aryl, or substituted or unsubstituted C ３～３０ Selected from heteroaryls, Each R ４ These are, independently, hydrogen, fluorine, hydroxyl, substituted or unsubstituted C １～２０ Alkyl, substituted, or unsubstituted C １～２０ Heteroalkyl, substituted, or unsubstituted C ６～３０ Aryl, or substituted or unsubstituted C ３～３０ Selected from heteroaryls, Two R's １ Together Cy １ They may form a fused ring, and the fused ring may optionally further contain one or more divalent linking groups as part of its structure. One Z １ and one R １ They will be together and arbitrarily Cy １ They may form a fused ring, and the fused ring may optionally further contain one or more divalent linking groups as part of its structure. Each of a and b is an independent integer between 0 and 2, but the sum of a and b is 1 or greater. c is an integer between 0 and 10. d is an integer between 1 and 3. e is either 0 or 1, (The condition is that n is an integer between 0 and 4.)

2. Ring A １ However, single ring type C ３～６０ Aromatic group or polycyclic carbon ６～６０ The thermal acid generating compound according to claim 1, wherein the compound is an aromatic group.

3. Ring A １ However, C ３～１５ Monocyclic aliphatic group or C ６～１５ The thermoacid generator compound according to claim 1 or 2, wherein the compound is a polycyclic aliphatic group.

4. L １ A thermoacid generator compound according to any one of claims 1 to 3, wherein the bond is a single bond.

5. The thermoacid generator compound according to any one of claims 1 to 4, wherein the nitrogen-containing cation is ammonium or pyridinium.

6. A thermal acid generator compound according to any one of claims 1 to 5, wherein at least one anionic stabilizing group comprises -OH.

7. The thermal acid generating compound according to any one of claims 1 to 6, wherein the anion does not contain a trifluoromethyl group and a difluoromethylene group.

8. The thermal acid generating compound according to any one of claims 1 to 7, wherein the anion does not contain fluorine.

9. The thermoacid generator compound according to any one of claims 1 to 8, wherein the thermoacid generator compound is polymerizable.

10. A thermal acid generator according to any one of claims 1 to 9; polymers and; With a solvent; A coating composition containing the following:

11. A pattern formation method, A layer of the coating composition described in claim 10 is applied to a substrate to obtain a lower layer composition; To cure the aforementioned lower layer composition to form a lower layer film; A photoresist composition layer is obtained by coating a layer of the photoresist composition onto the underlying film; Obtaining an exposed photoresist composition layer by pattern-like exposure of the photoresist composition layer with activating radiation; and The exposed photoresist composition layer is developed to obtain a resist relief image; Methods that include...

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