Polymerizable compound, photoresist composition, and pattern forming method

Abstract

The present invention provides polymerizable compounds, photoresist compositions, and pattern formation methods. [Solution] A polymerizable compound comprising an anion; a cation; and a polymerizable group bonded to the anion or cation, wherein the anion is (i) a monocyclic or polycyclic C having a first substituent. 3~60 (ii) an anion-stabilizing group comprising an aromatic group and (ii) an anion-stabilizing group, wherein the first substituent comprises an anion group, the anion group being selected from a sulfonate anion group, a sulfinate anion group, a sulfonimide anion group, a sulfamate anion group, or a sulfonamide anion group, the anion-stabilizing group being configured to form an intramolecular non-covalent bond with the anion group, and the first substituent further comprises an anion-stabilizing group, or a monocyclic or polycyclic C 3~60 A polymerizable compound in which the aromatic group further contains a second substituent, the second substituent containing an anion-stabilizing group.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority and interest in U.S. Provisional Patent Application No. 63 / 758,733, filed with the U.S. Patent and Trademark Office on 14 February 2025, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to polymerizable compounds, photoresist compositions, and patterning methods using such photoresist compositions. The present invention finds particular applicability to lithography applications in the semiconductor manufacturing industry. [Background technology]

[0003] A photoresist composition is a photosensitive material used to transfer a pattern onto one or more underlying layers, such as metal, semiconductor, or dielectric layers, placed on a substrate. Positive-type chemically amplified photoresist compositions have traditionally been used for high-resolution processing. Such resist compositions typically contain a polymer having acid-unstable groups and a photoacid generator (PAG). A layer of the photoresist composition is exposed to activating radiation in a patterned manner, and the PAG generates acid in the exposed areas. During post-exposure baking, the acid causes cleavage of the acid-unstable groups of the polymer in the exposed areas and a resulting polarity switch of the polymer. This creates a difference in solubility characteristics between the exposed and unexposed areas of the photoresist layer in the developer solution. In a positive-type development (PTD) process, the exposed areas of the photoresist layer become soluble in the developer, typically an aqueous base developer, and are removed from the substrate surface, while the unexposed areas remain on the substrate, forming a positive relief image. Alternatively, in a negative development (NTD) process, unexposed areas of the photoresist layer can be removed with an organic solvent developer, typically n-butyl acetate, while exposed areas remain on the substrate, forming a negative relief image. The resulting relief image allows for selective processing of the substrate.

[0004] A property of photoresist compositions that can directly impact semiconductor manufacturing costs is photosensitivity, i.e., sensitivity to activating radiation generated by exposure tools; higher sensitivity corresponds to higher process throughput for a given shape. To increase photosensitivity, it is desirable that the PAG generates an acid strong enough to cleave acid-unstable groups on the polymer. For this purpose, ionic PAG compounds having photoactive cations and anions with fluorinated sulfonate groups are typical, where the fluorine atom and / or fluoroalkyl group are very close to the sulfonate group, typically bonded as substituents to one or more alkylene carbon atoms bonded to a sulfonate anion group. Upon exposure to activating radiation, the photoactive cation undergoes a series of photochemical and chemical processes that lead to the formation of fluorinated sulfonic acid. Certain fluorinated PAGs in this class of compounds enable highly acidic photoacids, and there is growing interest from the semiconductor manufacturing industry and government regulatory bodies in replacing them with more sustainable alternatives.

[0005] Examples of existing fluorine-free PAGs include the p-toluenesulfonate anion and the camphor sulfonic acid anion. However, these anions have relatively low acid dissociation constants (e.g., about 18 orders of magnitude smaller than those of tris(tolufluoromethylsulfonyl)methane), which limits their usefulness in photoresists requiring higher photoacidity. Therefore, it would be desirable to have a photoresist composition containing an ionic photoacid generator compound that generates a sufficiently strong sulfonic acid without relying on specific fluorine substitutions for increased acidity. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] U.S. Patent No. 8,431,325 [Patent Document 2] U.S. Patent No. 4,189,323 [Overview of the project] [Problems that the invention aims to solve]

[0007] There is a continuous need for photoresist compositions that address one or more problems associated with cutting-edge technologies, and for patterning methods using such photoresist compositions. [Means for solving the problem]

[0008] One embodiment is a polymerizable compound comprising an anion; a cation; and a polymerizable group bonded to the anion or cation, wherein the anion is (i) a monocyclic or polycyclic C having a first substituent. 3~60 (ii) an anion-stabilizing group comprising an aromatic group and (ii) an anion-stabilizing group, wherein the first substituent comprises an anion group, the anion group being selected from a sulfonate anion group, a sulfinate anion group, a sulfonimide anion group, a sulfamate anion group, or a sulfonamide anion group, the anion-stabilizing group being configured to form an intramolecular non-covalent bond with the anion group, and the first substituent further comprises an anion-stabilizing group, or a monocyclic or polycyclic C 3~60 The present invention provides a polymerizable compound in which the aromatic group further comprises a second substituent, the second substituent comprising an anion-stabilizing group.

[0009] Another embodiment provides a photoresist composition comprising a polymerizable compound, or a polymer containing repeating units derived from a polymerizable compound, and a solvent.

[0010] Another embodiment provides a pattern forming method comprising: coating a layer of photoresist composition onto a substrate to provide a photoresist composition layer; exposing the photoresist composition layer to activating radiation in a patterned manner to provide an exposed photoresist composition layer; and developing the exposed photoresist composition layer to provide a resist relief image. [Modes for carrying out the invention]

[0011] Exemplary embodiments will be described in detail below, and examples thereof are illustrated in this description. In this regard, these exemplary embodiments may take different forms and should not be construed as being limited to the descriptions expressed herein. Accordingly, the exemplary embodiments are described below only to illustrate aspects of this description. As used herein, the terms “and / or” encompass any and all combinations of one or more of the enumerated items relating to the description. 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.

[0012] 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 indicated herein or unless the context clearly contradicts this. “Or” means “and / or” unless otherwise clearly indicated. 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 can be independently combined 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., in this specification 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 exists. 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.

[0013] Unless otherwise defined, 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 present invention pertains. Terms, such as those defined in commonly used dictionaries, should be construed to have meanings consistent with those in the relevant art and in relation to this disclosure, and it will be further understood that they should not be construed in an ideal or overly formal sense unless explicitly defined herein.

[0014] In this specification, "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, particle beams such as electron beams and 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, sometimes 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.

[0015] As used herein, the terms “hydrocarbon” means an organic compound or organic group 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 A "carboxylic acid group" refers to a group having the formula "-C(O)-OH"; a "cycloalkyl" refers to a monovalent group having one or more saturated rings in which all ring members are carbon; a "cycloalkylene" refers to a cycloalkyl group with a valency of 2; an "alkenyl" refers to a monovalent hydrocarbon group having at least one carbon-carbon double bond, either in a straight or branched chain; an "alkenoxy" refers to "alkenyl-O-"; an "alkenylene" refers to an alkenyl group with a valency of 2; a "cycloalkenyl" refers to a group having at least one carbon "Alkynyl" refers to a non-aromatic cyclic monovalent hydrocarbon group having at least three carbon atoms along with a primary-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; "Alkynyl" refers to a monovalent hydrocarbon group having at least one carbon atom along with a primary-carbon double bond; "Arylene" 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 a divalent aryl group; "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-".

[0016] 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, where each heteroatom is 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" and "heteroaryl" refer to heterocycloalkyl groups having a valence of 2; "heteroaryl" refer to aromatic 4-8 member monocyclic, 8-12 member bicyclic, or 11-14 member tricyclic ring systems having 1-4 heteroatoms (for monocyclics), 1-6 heteroatoms (for bicyclics), or 1-9 heteroatoms (for tricyclics) (for example, in the case of monocyclics, bicyclics, or tricyclics, carbon atoms and 1-3, 1-6, or 1-9 heteroatoms of N, O, or S, respectively). Examples of heteroaryl groups include pyridyl, furyl (furyl or furanyl), imidazolyl, benzimidazolyl, pyrimidinyl, thiophenyl or thienyl, quinolinyl, indolyl, thiazolyl, etc.; "heteroarylene" refers to heteroaryl groups having a valence of 2.

[0017] 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. Combinations of halo groups (e.g., bromo and fluoro) or fluoro groups 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. 1~8Refers to an alkyl group, which is further substituted with one or more other substituents that are not halogen. Since a halogen atom does not replace a carbon atom, it should be understood that substitution of a group with a halogen atom is not considered a heteroatom-containing group.

[0018] Each of the aforementioned substituents may be optionally substituted, unless otherwise specifically defined. The term "optionally substituted" refers to being either substituted or unsubstituted. "Substituted" means that at least one hydrogen atom of a chemical structure or group is replaced with another terminal substituent, typically monovalent, provided that it does not exceed the normal valence of the specified atom. When the substituent is oxo (i.e., O), two geminal hydrogen atoms on a carbon atom are replaced with a terminal oxo group. It is further pointed out that the oxo group is bonded to carbon via a double bond to form a carbonyl (C=O), and in this case the carbonyl group is represented as -C(O)- herein. Combinations of substituents or variables are permitted. Exemplary substituents that may be present at a "substituted" position include nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (O), amino (-NH2), mono- or di-(C 1~6 )alkylamino, alkanoyl (such as acyl, etc. C 2~6 alkanoyl group, etc.), formyl (-C(O)H), carboxylic acid or its alkali metal or ammonium salt; C 2~6 alkyl ester (-C(O)O-alkyl or -OC(O)-alkyl) and C 7~13 aryl ester (-C(O)O-aryl or -OC(O)-aryl), etc. esters (including acrylates, methacrylates, and lactones); amide (-C(O)NR2, wherein R is hydrogen or C 1~6 alkyl), carboxamide (-CH2C(O)NR2, wherein R is hydrogen or C 1~6 alkyl), halogen, thiol (-SH), C 1~6 alkylthio (-S-alkyl), thiocyanato (-SCN), C 1~6 alkyl, C 2~6 alkenyl, C 2~6Alkinyl, C 1~6 Haloalkyl, C 1~9 Alkoxy, C 1~6 Haloalkoxy, C 3~12 Cycloalkyl, C 5~18 Cycloalkenyl, C 2~18 Heterocycloalkenyl, a C2 compound having at least one aromatic ring. 6~12 Aryl (e.g., phenyl, biphenyl, naphthyl, etc., where each ring is either substituted or unsubstituted aromatic), 1 to 3 separate rings or fused rings, and C having 6 to 18 ring carbon atoms. 7~19 Arylalkyls, arylalkoxys having 1 to 3 separate rings or fused rings and 6 to 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 This includes, but is not limited to, arylsulfonyl (-S(O)2-aryl) or tosyl (CH3C6H4SO2-).

[0019] As used herein, unless otherwise specified, "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 C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C3~30 It is a heteroaryl compound. Typically, the divalent linking groups are -O-, -S-, -C(O)-, -C(O)O-, -N(R')-, and -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 heteroarylenes or combinations thereof, where R' is 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. More typically, the divalent linking group is -O-, -C(O)-, -C(O)O-, -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution 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 The compound comprises at least one heteroarylene or combination thereof, where 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 It is a heteroaryl compound.

[0020] As used herein, “acid-unstable group” refers to a group whose bonds are selectively 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 selectively 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, 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. Acid-unstable groups are also commonly referred to in this art as "acid-cleavable groups," "acid-cleavable protecting groups," "acid-unstable protecting groups," "acid-leaving groups," "acid-degradable groups," and "acid-sensitive groups."

[0021] The sensitivity of photoresist performance often correlates with the final device production throughput. In particular, high-resolution lithography techniques, such as 193nm lithography (ArF), tend to struggle with photoresists that have optimal sensitivity. To achieve good sensitivity, many photoresists use photoacid generators (PAGs) containing anions belonging to the sulfonate class linked to polymers containing low-activation-energy leaving groups (e.g., ester acetals or acetal-esters). Over the past decade or so, many sulfonate derivatives have been developed for this purpose, with fluorinated sulfonates being one example. These compounds, which excel in lithography thanks to their remarkably high acidity, are being considered for replacement globally in favor of more sustainable alternatives. However, there is still a continued need for PAG anions with good acidity and better sustainability.

[0022] The inventors have discovered a photoacid generator comprising an anionic core containing (i) an anionic group and (ii) an aromatic group substituted with an anionic stabilizing group configured to stabilize the anionic group by an intramolecular non-covalent bond. In other words, the anionic stabilizing group is configured to form an intramolecular non-covalent bond with the anionic group. For example, without wishing to be bound by theory, the anionic stabilizing group can form an intramolecular non-covalent bond with the anionic group, or for example, the anionic stabilizing group may form an intramolecular non-covalent bond with the anionic group. In some embodiments, the intramolecular non-covalent bond may be formed in situ, such as when a nonpolymeric ionic photoacid generator compound is included in a photoresist composition. When used in a photoresist composition, the PAG according to the present invention has a sizing energy (E サイズ This can lead to favorable lithography characteristics such as exposure tolerance (EL%) and / or line width roughness.

[0023] A polymerizable compound is provided comprising an anion; a cation; and a polymerizable group bonded to the anion and the cation. The anion is (i) a monocyclic or polycyclic C containing a first substituent. 3~60 The molecule comprises an aromatic group and (ii) an anion-stabilizing group. The first substituent comprises an anion group, which is selected from a sulfonate anion group, a sulfinate anion group, a sulfonimide anion group, a sulfamate anion group, or a sulfonamide anion group. The anion-stabilizing group is configured to form an intramolecular non-covalent bond with the anion group, where the first substituent further comprises an anion-stabilizing group or a monocyclic or polycyclic C 3~60 The aromatic group further comprises a second substituent, the second substituent comprising an anion-stabilizing group. The anion-stabilizing group may be part of the first substituent, or the anion-stabilizing group may be monocyclic or polycyclic C 3~60 It may be part of the second substituent of the aromatic group.

[0024] As used herein, “anion stabilizing group” refers to any suitable group that can stabilize an anionic group via intramolecular non-covalent bonding, such as those provided herein. Thus, anion stabilizing group is configured to form intramolecular non-covalent bonding with an anionic group, or in other words, anion stabilizing group can form intramolecular non-covalent bonding with an anionic group. As used herein, “non-covalent bonding” may refer to any non-covalent interaction between anion stabilizing group and an anionic group. As noted above, non-covalent interactions are intramolecular, and the anion stabilizing group and the anionic group are on the same molecule. Exemplary non-covalent bonding includes hydrogen bonding or ionic bonding. Anion stabilizing groups may include protic groups. For example, intramolecular non-covalent bonding may be intramolecular hydrogen bonding between suitable hydrogen atoms of the anion stabilizing group and the anionic group. For example, in some embodiments, anion stabilizing group may be configured to form intramolecular hydrogen bonding with an anionic group, and for example, in some embodiments, anion stabilizing group can form intramolecular hydrogen bonding with an anionic group. In some embodiments, intramolecular hydrogen bonding includes dipole-dipole interactions, ion-dipole interactions, or a combination thereof. As used herein, “non-covalent bonding” does not include bonding based solely on van der Waals forces.

[0025] Polymerizable groups further enable the incorporation of photoacid generators into the repeating units of the polymer. Incorporation of PAG into the polymer can further suppress acid diffusion during resist heat treatment, for example, by physically confining the PAG component to the rest of the polymer. Thus, PAG diffusion is effectively limited, which can reduce acid diffusion blur and improve resolution and pattern roughness. It is understood that the suppression of acid diffusion can be manifested as an increase in contrast curve dose-to-clear or pattern formation dose-to-size. In addition, the binding of PAG moieties to polymer chains provides a more uniform spatial distribution of PAG moieties throughout the resulting film, thus minimizing the randomness or stochastic effects typically encountered with small molecule PAGs in conventional chemically amplified resists.

[0026] In some embodiments, the polymerizable group is bonded to an anion. For example, the anion is of formula (1): [ka] It can be represented as follows.

[0027] In equation (1), Ar l This is a monocyclic or polycyclic C 3~60 It is an aromatic group. For example, monocyclic or polycyclic carbon atoms. 3~60 Aromatic groups are monocyclic C 3~60 Aromatic group or polycyclic carbon 6~60 It may be an aromatic group. In some embodiments, it may be a monocyclic or polycyclic carbon. 3~60 Aromatic groups are monocyclic or polycyclic carbon groups. 6~60 Arirene group or monocyclic or polycyclic C 3~60 Heterarylene groups, typically monocyclic or polycyclic C 6~30 Arylene group or monocyclic or polycyclic C 3~30 It may be a heteroarylene group.

[0028] "Single-ring or multi-ring C" 6~60 When an "arylene group" is polycyclic, it should be understood that the number of carbon atoms is sufficient for the group to be chemically feasible. For example, "monocyclic or polycyclic C 6~60 "Arylene group" refers to "monocyclic C6 arylene group or polycyclic C6 group". 10~60 Arylene group; or, for example, monocyclic C6 arylene group or polycyclic C6 group 10~30 It can refer to an "arylene group". Similarly, it can refer to a "monocyclic or polycyclic carbon group". 3~60 If the heteroarylene group is polycyclic, the number of carbon atoms is sufficient for the group to be chemically realizable. For example, monocyclic or polycyclic C 3~60 "Heterorialene group" is a "monocyclic C 3~6 Heteroarylene group or polycyclic C 5~60 It could refer to a "heteroarylene group"; or, for example, a "monocyclic C 3~6 Heteroarylene group or polycyclic C 5~30can refer to a "heteroarylene group".

[0029] Exemplary monocyclic or polycyclic C 3~60 Aromatic groups include, but are not limited to, benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylene, chrysene, phenalene, benz[a]anthracene, dibenz[a,h]anthracene, or benzo[a]pyrene.

[0030] In formula (1), each L 1 is independently a single bond or one or more divalent linking groups, where L 1 does not contain fluorine. In other words, when L 1 is one or more divalent linking groups, L 1 does not contain fluorine. Each of the one or more divalent linking groups may be substituted or unsubstituted. Exemplary divalent linking groups are each independently -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, -N(R ’ )-, -C(O)N(R’)-, 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 a combination thereof, where R ’ is 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 heteroaryl. Typically, L 1 is a single bond or substituted or unsubstituted C 1~20 alkylene, preferably a single bond or substituted or unsubstituted C 1~10 alkylene, where L 1It does not contain an α-carbon atom that is directly covalently bonded to the sulfur atom of a sulfonate anion group substituted with a fluorine atom or a fluoroalkyl group.

[0031] If b is 0, L 1 L can be a single bond or one or more linking groups, where L 1 It should be understood that it does not contain fluorine.

[0032] 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 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarylenes or combinations thereof may be selected, where R ’ C is 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 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 3~30It comprises one or more divalent linking groups selected from heteroarylenes or combinations thereof, where each 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. In some embodiments, L 2 It contains an iodo-substituted aromatic group.

[0033] In equation (1), each R 1 R is independently a monovalent nonhydrogen substituent; where each R 1 It optionally further includes one or more divalent linking groups as part of its structure. For example, each R 1 These are, independently, halogens, hydroxyls, 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 It can be a heteroaryloxy. 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 C7~30 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 It may be a heteroaryloxy. In some embodiments, at least one R 1 is substitution C 6~30 Aryl or substituted C 7~30 It is an arylalkyl. In some embodiments, at least one R 1 It contains a halogen atom, such as a fluoro or iodo group, as part of its structure.

[0034] In equation (1), each R 1 The compound optionally further includes 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-, 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 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarylenes or combinations thereof may be selected, where R ’ C is 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 could be a heteroaryl.

[0035] In some embodiments, one or more R 1Each of these may independently contain an acid-unstable group, a lactone-containing group, a base-solubilizing group, or a combination thereof.

[0036] In equation (1), each Z 1 It independently contains an anion stabilizing group, where at least one Z 1 It is configured to form a ring having 5 to 8 atoms by forming an intramolecular non-covalent bond with a sulfonate anion, Z 1 These are independently -OH, -C(O)OH, -SH, -C(O)SH, and -NHS(O)2R 2 -S(O)2R 2 ,-S(O)R 2 -S(O)2NHS(O)2R 2 -CH (=NOH), or -B (R 3 ) Selected from 2; each Z 1 It optionally further includes 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 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.

[0038] In some embodiments, each anion stabilizing group includes a protic group. For example, if the anion stabilizing group is protic, each Z 1 These are independently -OH, -C(O)OH, -SH, -C(O)SH, and -NHS(O)2R 2 -S(O)2R 2a -S(O)2NHS(O)2R 2 -CH (=NOH), or -B (R 2a ) can be selected from 2, where each R 2 These are, independently, fluorine, hydroxyl, 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 R 2a is hydroxyl; each R 3a 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 heteroaryl compounds, but with at least one R 3a This is conditional on it being hydrogen or hydroxyl.

[0039] In equation (1), each Z 1 The compound optionally further includes 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-, 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 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarylenes or combinations thereof may be selected, where R ’ C is 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 can be a heteroaryl compound. Typically, Z 1 These are, arbitrarily selected, -O-, -C(O)-, -C(O)O-, -S(O)-, -S(O)2-, and -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~10 Alkylene, substituted or unsubstituted C 3~10Cycloalkylene, substituted or unsubstituted C 3~10 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 The material further comprises one or more divalent linking groups selected from heteroarylenes or combinations thereof, where R ’ C is 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 could be a heteroaryl.

[0040] In equation (1), each R 2 These are independently fluorine, 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.

[0041] In equation (1), each R 2a 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.

[0042] In equation (1), the two R 1 Ar 1 A fused ring is formed, where the fused ring optionally further includes one or more divalent linking groups as part of its structure. Each of the one or more divalent linking groups is either substituted or unsubstituted, and the fused ring is either substituted or unsubstituted.

[0043] In equation (1), one Z 1 and one R 1Ar 1 Ar forms a fused ring, where the fused ring optionally further includes one or more divalent linking groups as part of its structure. Each of the one or more divalent linking groups is either substituted or unsubstituted, and the fused ring is either substituted or unsubstituted. 1 The condensed ring formed may be aliphatic or aromatic.

[0044] In formula (1), P is a polymerizable group. Exemplary 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.

[0045] In equation (1), each a and b is an independent integer between 0 and 2, provided that the sum of a and b is 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), d is an integer between 1 and 3. Typically, d is 1 or 2, preferably d is 1. For example, in some embodiments, a can be 1 or 2 and d can be 1. In some embodiments, d can 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 some embodiments, Ar 1 This is a single ring C 3~60 It can be an aromatic group and has at least one Z 1 is, -L 1 -SO3 - It is located in the ortho position relative to the group represented by . For example, Ar 1 This is a single ring C 3~6It can be an aromatic group, and at least one Z1 is -L 1 -SO3 - It can be in the ortho position relative to the group represented by . In some embodiments, Ar 1 This is a single ring C 3~6 It can be a compound group, L 1 It is a single bond, and at least one Z1 is -L 1 -SO3 - It can be in the ortho position relative to the group represented by .

[0049] In some embodiments, Ar 1 This is a polycyclic C 6~60 It can be an aromatic group and has at least one Z 1 The base is -L 1 -SO3 - For the group represented by the same ring, the Ar at the ortho position 1 It can bond to the ring carbon atoms. For example, Ar 1 This is a polycyclic C 6~60 It can be a compound group, L 1 It is a single bond and has at least one Z 1 The base is -L 1 -SO3 - For the group represented by the same ring, the Ar at the ortho position 1 It can bond to the ring carbon atoms.

[0050] In some embodiments, in formula (1), Ar 1 This is a polycyclic C 6~60 It can be an aromatic group and has at least one Z 1 The base is -L 1 -SO3 - The Ar at the β position with respect to the ring carbon atom to which it is bonded. 1 A carbon atom may bond to at least one Z 1 Base and -L 1- SO3 - These substituents are bonded to different rings of the polycyclic aromatic group. As used herein, the term "beta substituent" refers to a substituent bonded to each aromatic ring carbon atom on different rings of a polycyclic ring system, the ring carbon atoms being separated by the bonded ring carbon atoms.

[0051] In some embodiments, the anion is given by formula (1a): [ka] (In the formula, Ar 1 , R 1 , Z 1 , L 1 , L 2 (P, a, c, and d are as defined for equation (1), respectively.) It can be represented as follows.

[0052] In some embodiments, the anion is given by formula (1b): [ka] (In the formula, Ar 1 , R 1 , Z 1 , L 1 , L 2 (P, b, c, and d are as defined for equation (1), respectively.) It belongs to them.

[0053] Examples of anions represented by formula (1) include the following: [ka] [ka] [ka] It includes.

[0054] 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).

[0055] In some embodiments, the polymerizable group is bonded to the cation of the polymerizable compound. For example, the anion is of formula (2): [ka] (In the formula, Ar 1 , R 1 , Z 1 , Z 2 , L 1 , L 2 (P, a, b, c, and d are as defined for equation (1)) It can be represented as follows.

[0056] Examples of anions represented by formula (2) include the following: [ka] [ka] [ka] [ka] [ka] [ka] It includes.

[0057] In some embodiments, the conjugate acid of the polymerizable compound anion may have a pKa of 0 or less. Typically, the conjugate acid may have a pKa of -2 or less, preferably -5 or less. The conjugate acid may have a pKa of, for example, -15 to 0 or -15 to -2.

[0058] The anions of the photoacid-generating compounds may be obtained from commercial sources or prepared by any preferred method. For example, such anions may be prepared as described in the examples herein.

[0059] Polymerizable compounds further contain cations. It should be understood that if the anionic moiety does not contain a polymerizable group, the cationic moiety will contain a polymerizable group as part of its structure. In some embodiments, both the cation and the anion contain a polymerizable group as part of their structure.

[0060] Any suitable cation may be used. Exemplary cations may include, but embodiments are not limited to, ammonium, pyridinium, iodonium, and sulfonium.

[0061] In some embodiments, the cation is a sulfonium cation of formula (3a) or an iodonium cation of formula (3b): [ka] It is possible.

[0062] In equations (3a) and (3b), R 10 ~R 14 These are, independently, substituted or non-substituted C 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 2~30 Alkenyl, substituted, or unsubstituted C 2~30 Alkinyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 7~30 Arylalkyl, or substituted or unsubstituted C 4~30 It is a heteroarylalkyl group, or a combination thereof. 10 ~R 14 Each of these may be separate or connected to another group R via a single bond or divalent linking group. 10 ~R 14 It can either bond with R to form a ring. 10 ~R 14 Each of these may optionally include a divalent linking group as part of its structure. 10 ~R 14Each of these may independently optionally contain an acid-unstable group selected from, for example, a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of an alkyl group and an aryl group, a tertiary alkoxy group, an acetal group, or a ketal group. If the anion does not contain a polymerizable group, R 10 ~R 12 at least one of or R 13 ~R 14 At least one of these further includes a polymerizable group as part of its structure. 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.

[0063] Exemplary sulfonium cations of formula (3a) include the following: [ka] It may include one or more of the following.

[0064] Examples of iodonium cations in formula (3b) include the following: [ka] It may include one or more of the following.

[0065] Examples of cations containing polymerizable groups include: [ka] (In the formula, each R d These are, independently, hydrogen, deuterium, fluorine, cyano, or substituted or unsubstituted C 1~10 It is alkyl. Preferably, R d is hydrogen, fluorine, or substituted or unsubstituted C 1~5 Alkyl, typically methyl) It includes.

[0066] Cationic compounds for polymerizable compounds can be obtained from commercial sources or prepared using common synthetic procedures.

[0067] Suitable polymerizable compounds include those resulting from any combination of the anions and cations described above. Polymerizable compounds can be prepared by combining an anionic species with a cationic species under appropriate conditions.

[0068] Another embodiment provides a polymer comprising repeating units derived from a polymerizable compound. Other repeating units, such as those described herein for repeating units of non-solvent alkali-insoluble base polymers, may be included in the polymer.

[0069] A photoresist composition is also provided which comprises a polymerizable compound, or a polymer containing repeating units derived from a polymerizable compound, and a solvent. That is, the photoresist composition may (i) comprise a polymerizable compound and a solvent, or (ii) comprise a polymer containing repeating units derived from a polymerizable compound and a solvent.

[0070] Polymerizable compounds may be present in the photoresist composition in amounts of 1 to 99 weight percent (wt%), more typically 1 to 80 weight%, 2 to 75 weight%, or 2 to 60 weight%, based on the total solids content of the photoresist composition.

[0071] If the photoresist composition contains a polymer comprising repeating units derived from a polymerizable compound, the polymer may be present in the photoresist composition in an amount of 1 to 99 weight percent (wt%), more typically 1 to 80 weight%, 2 to 75 weight%, or 2 to 60 weight%, based on the total solids content of the photoresist composition.

[0072] Repeating units of polymers, including units derived from polymerizable compounds, may typically be present in amounts of 1–100 mol%, typically 1–55 mol%, and more typically 2–25 mol%, relative to the total repeating units of the polymer. Other repeating units, such as those described herein for repeating units of non-solvent alkali-insoluble substrate polymers, may be present in the polymer.

[0073] Exemplary polymers containing repeating units derived from polymerizable compounds include the following: [ka] (In the formula, a, b, and c represent the mole fractions for each repeating unit of the polymer, and a + b + c = 1) It includes.

[0074] The polymer typically has a weight-average molecular weight (M) of 1,000 to 200,000 Datons (Da), preferably 10,000 to 150,000 Da, more preferably 15,000 to 150,000 Da, and even more preferably 25,000 to 150,000 Da or 50,000 to 150,000 Da. w ) has M w Logarithmic mean molecular weight (M n The polydispersity index (PDI) of the polymer, which is the ratio of ), is typically 1.1–3, more typically 1.1–2. The molecular weight is determined by gel permeation chromatography (GPC) using a polystyrene standard.

[0075] Polymers can be prepared using any suitable method in the art. For example, one or more monomers corresponding to the repeating units described herein can be combined or supplied separately using a suitable solvent and initiator and polymerized in a reactor. For example, polymers can be obtained by polymerization of each monomer under any suitable conditions, such as heating at an effective temperature, irradiation with chemical rays at an effective wavelength, or a combination thereof.

[0076] The photoresist composition further comprises an additional photoacid generator distinct from the polymerizable compound. The additional PAG may be in polymeric or nonpolymeric form. In polymeric form, the additional PAG may exist as a portion of repeating units of a polymer derived from a polymerizable PAG monomer.

[0077] A suitable additional PAG compound is formula G + A - (In the formula, G + A is a photoactive cation, - The photoactive cation may be an anion capable of generating photoacid. The photoactive cation is preferably an onium cation, preferably an iodonium cation or sulfonium cation, such as those mentioned above with respect to the nonpolymeric ionic photoacid generator compound of the present invention (e.g., those of formula (3a) and / or (3b)). Particularly preferred anions include those whose conjugate acid has a pKa of -15 to 0, or -14 to 0, or -13 to 0. The anions are typically organic anions having a sulfonate group or a nonsulfonate-type group, such as sulfonamide, sulfonimidate, methide, arsenate, or borate. In some embodiments, the additional PAG may have an anion having the structure of formula (1) as defined for the anion of the nonpolymeric ionic photoacid generator compound, where the anion of the additional PAG compound has the anion stabilizing group Z 1 It does not include.

[0078] In some embodiments, the anions of the additional PAG do not contain -F, -CF3, or -CF2- groups, and are absent. “Do not contain -F, -CF3, or -CF2- groups” should be understood to mean that the anions of the additional PAG exclude groups such as -CH2CF3 and -CH2CF2CH3. In yet other embodiments, the anions of the additional PAG are fluorine-free (i.e., they do not contain fluorine atoms and are not substituted by fluorine-containing groups). In some embodiments, the additional PAG is fluorine-free (i.e., both the photoactive cation and anion are fluorine-free).

[0079] Exemplary onium salts may include, for example, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; di-t-butylphenyliodonium perfluorobutanesulfonate, and di-t-butylphenyliodonium camphorsulfonate. Other useful additional PAG compounds known in the field of chemically amplified photoresists include, for example: nonionic sulfonyl compounds, e.g., 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters, e.g., 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, e.g., bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl) The PAGs include diazomethane; glyoxime derivatives, such as bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime; sulfonic acid ester derivatives of N-hydroxyimide compounds, such as N-hydroxysuccinidomethanesulfonic acid and N-hydroxysuccinidomitetrifluoromethanesulfonic acid; and halogen-containing triazine compounds, such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine. Further suitable PAGs are described in (Patent Document 1) and (Patent Document 2).

[0080] Typically, when a photoresist composition contains additional PAGs, the additional PAGs are present in the photoresist composition in an amount of 0.1 to 55% by weight, more typically 1 to 25% by weight, based on the total solids content of the photoresist composition. When present in polymer form, the additional PAGs are typically present in the polymer in an amount of 1 to 25 mol%, more typically 1 to 8 mol%, or 2 to 6 mol%, based on the total repeating units in the polymer.

[0081] The photoresist composition may also contain one or more non-solvent alkali-insoluble substrates, which typically exist in a total amount of more than 50% by weight based on the total solids content of the photoresist composition. These one or more non-solvent alkali-insoluble substrates, which may be referred to herein as matrix materials, may be polymers or nonpolymers. Suitable alkali-insoluble substrates will be apparent to those skilled in the art and are based on the descriptions provided herein. In some embodiments, the alkali-insoluble substrates are free of phenolic hydroxyl groups, such as phenolic hydroxyl group-containing novolac resins. In some embodiments, the alkali-insoluble substrates are free of carboxylic acid groups. In some embodiments, the alkali-insoluble substrates may contain phenolic hydroxyl groups and / or carboxylic acid groups, provided that the alkali-insolubility of the substrates is maintained. As noted above, the matrix material may also be a polymer containing repeating units derived from polymerizable compounds described herein.

[0082] To determine whether a particular substrate is alkali-insoluble, the substrate can be subjected to a solubility test in an aqueous alkaline developer solution, such as 0.26 N (N) aqueous tetramethylammonium hydroxide (TMAH). Alkali solubility can be determined, for example, by the following method: A film of the substrate can be applied to the surface of a Si substrate by spin coating, and the initial film thickness can be measured. The film of the substrate is immersed in a 0.26 N TMAH aqueous solution for 60 seconds at room temperature under typical developing conditions, followed by a DI water rinse and air drying, and then the film thickness is measured again. Alkali insolubility is indicated by a thickness change of less than 2 nanometers (nm), preferably less than 1 nm, less than 0.5 nm, less than 0.1 nm, or 0 nm.

[0083] In some embodiments, the substrate may include polymers, metal-containing materials, or combinations thereof. It should be understood that “substrate” does not define the material as basic (for example, the substrate is not necessarily basic according to the definition of acid / base chemistry).

[0084] The polymer of the photoresist composition may be a homopolymer or a copolymer comprising two or more structurally distinct repeating units. For example, the polymer may comprise one or more repeating units comprising functional groups selected from hydroxyaryl groups, acid-unstable groups, base-solubilizing groups, lactone-containing groups, sultone-containing groups, polar groups, crosslinking groups, etc., or combinations thereof. As noted above, the polymer may also comprise repeating units derived from polymerizable compounds described herein.

[0085] In one or more embodiments, the polymer may comprise repeating units formed from monomers containing acid-unstable groups. Suitable acid-unstable groups include, for example, tertiary esters, acetals, ketals, and tertiary ether groups. [ka] [ka] In the formula, R dThis includes hydrogen, halogens (e.g., F, Cl, Br, I), and substituted or unsubstituted C. 1~6 Alkyl, or substituted or unsubstituted C 3~6 It is a cycloalkyl group.

[0086] When repeating units with acid-unstable groups are present in a polymer, they typically exist in amounts of 25–75 mol%, more typically 25–50 mol%, and even more typically 30–50 mol%, relative to the total repeating units in the polymer.

[0087] In some embodiments, the polymer may contain repeating units derived from one or more lactone-containing monomers. Suitable lactone-containing monomers include, for example: [ka] (In the formula, R d This includes hydrogen, halogens (e.g., F, Cl, Br, I), and substituted or unsubstituted C. 1~6 Alkyl, or substituted or unsubstituted C 3~6 (It is cycloalkyl) It includes.

[0088] When repeating units derived from one or more lactone-containing monomers are present in the polymer, they are typically present in amounts of 0.5–75 mol%, more typically 1–50 mol%, and even more typically 5–50 mol%, relative to the total repeating units in the polymer.

[0089] In some embodiments, the polymer may comprise repeating units having a base-solubilizing group and / or a pKa of 12 or less. Exemplary base-solubilizing groups may include fluoroalcohol groups, carboxylic acid groups, carboxymido groups, sulfonamide groups, or sulfonimide groups.

[0090] Non-limiting examples of monomers containing a base-solubilizing group include: [ka] [ka] [ka] (In the formula, R i This includes hydrogen, halogens (e.g., F, Cl, Br, I), and substituted or unsubstituted C. 1~6 Alkyl, or substituted or unsubstituted C 3~6 (It is cycloalkyl) These are some examples.

[0091] If repeating units having a base-solubilizing group and / or a pKa of 12 or less are present in the polymer, they are typically present in amounts of 0.5–30 mol%, more typically 15–25 mol%, and even more typically 5–10 mol%, based on the total repeating units in the polymer.

[0092] The polymer may optionally further contain one or more repeating units containing aromatic groups. For example, such repeating units include: [ka] (In the formula, R b This includes hydrogen, halogens (e.g., F, Cl, Br, I), and substituted or unsubstituted C. 1~6 Alkyl, or substituted or unsubstituted C 3~6 (It is cycloalkyl) It includes one or more of the following.

[0093] If present, the polymer typically contains aromatic group-containing repeating units in amounts of 1 to 80 mol%, more typically 5 to 75 mol%, and even more typically 5 to 50 mol%, based on the total repeating units in the polymer.

[0094] In some embodiments, the polymer optionally has the following structure: [ka] (In the formula, R dC is hydrogen, fluorine, cyano, substituted or unsubstituted C 1~10 (It is alkyl.) It may contain repeating units derived from acetal monomers that do not contain ester acetals, such as monomers.

[0095] If present, the polymer typically contains repeating units having acetal monomers that do not contain ester acetals, in amounts of 1 to 80 mol%, more typically 5 to 75 mol%, and even more typically 5 to 50 mol%, based on the total repeating units in the polymer.

[0096] The polymer may optionally further contain one or more additional repeating units. These additional repeating units may be for the purpose of modifying the properties of the photoresist composition, such as etch rate and solubility. Exemplary additional units may include those derived from one or more (meth)acrylates, vinyl aromatics, vinyl ethers, vinyl ketones, and / or vinyl ester monomers. If present in the polymer, the one or more additional repeating units may be used in an amount of 50 mol% or less, typically 3–50 mol%, based on the total repeating units of the polymer.

[0097] Non-exclusive exemplary polymers for non-solvent, alkali-insoluble substrates include the following: [ka] (In the formula, a, b, and c represent the mole fractions for each repeating unit of the polymer, and a + b + c = 1) It includes one or more of the following. It should be understood that the mole fractions of a, b, and c are selected so that the polymer is alkali-insoluble.

[0098] In some embodiments and as described in further detail above herein, the non-solvent alkali-insoluble substrate may be a polymer further comprising repeating units derived from the polymerizable compounds of the present invention. For example, the repeating units of the exemplary polymer described above may be replaced by repeating units derived from the polymerizable compounds of the present invention as described herein, or additional repeating units derived from the polymerizable compounds of the present invention, such as those described herein, may be added to the exemplary polymer described above.

[0099] In some embodiments, the non-solvent alkali-insoluble substrate may include chain-cleavable polymers, unclipping polymers, or combinations thereof.

[0100] Chain-cleavable polymers can undergo chain-cleavage reactions under suitable conditions. Any suitable chain-cleavable polymer can be used. Exemplary direct photolysis, chain-cleavable polymers include, for example, copolymers of α-substituted styrene and substituted α-halogenated acrylates, such as α-methylstyrene / methyl-α-chloroacrylate copolymer, 2-trifluoroel-α-chloroacrylate / α-methyl-4-fluorostyrene copolymer, etc., or combinations thereof.

[0101] Unzipping polymers include polymers that have unczipping polymer end groups when triggered by a suitable stimulus (photo-induced or chemically induced stimulus) that causes the polymer backbone to decompose into smaller parts. Typically, unczipping polymers are selected so that the stimulus of a first chemical modification or decomposition event triggers an unczipping effect, whether partial or complete. Any suitable unczipping polymer may be used.

[0102] The polymer typically has a molecular weight of 1,000 to 200,000 Da, preferably 10,000 to 150,000 Da, more preferably 15,000 to 150,000 Da, and even more preferably 25,000 to 150,000 Da or 50,000 to 150,000 Da. wIt has the following properties. The PDI of the polymer is typically 1.1–3, more typically 1.1–2. The molecular weight value is determined by GPC using polystyrene standards.

[0103] Polymers can be prepared using any suitable method in the art. For example, one or more monomers corresponding to the repeating units described herein can be combined using a suitable solvent and initiator, or supplied separately, and polymerized in a reactor. For example, polymers can be obtained by polymerization of each monomer under any suitable conditions, such as heating at an effective temperature, irradiation with chemical rays at an effective wavelength, or a combination thereof.

[0104] In some embodiments, one or more non-solvent alkali-insoluble substrates may be metal-containing materials. Exemplary metal-containing materials include organometallic resists (e.g., photo-induced crosslinkable organometallic resists), metal oxide resists, or combinations thereof. In some embodiments, the metal-containing material may include Sn, Zr, Hf, Si, Ge, Se, Cr, Mo, W, V, Nb, Ta, P, Sb, Ti, Ce, Ru, Sb, Y, Ga, Cr, Fe, Co, Ru, Al, In, Sc, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Zn, Co, Ni, Mn, Mg, Ca, Sr, Ba, or combinations thereof. Typically, the metal-containing material may include Sn, Zr, Hf, Si, Ge, Se, or combinations thereof.

[0105] One or more non-solvent alkali-insoluble substrates are present in a total amount exceeding 50% by weight based on the total solid content of the photoresist composition. For example, one or more non-solvent alkali-insoluble substrates may be present in a total amount of 50% to 99% by weight, typically 60% to 95% by weight, or 70% to 90% by weight, based on the total solid content of the photoresist composition.

[0106] A photoresist composition further comprises a solvent for dissolving the components of the composition and for facilitating its coating on a substrate. 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, and methyl isobutyl ketone. These include ketones such as 2-heptanone and 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 dimethyl carbonate, ethylene carbonate, propylene carbonate, and diphenyl carbonate; polar aprotic solvents such as dimethyl sulfoxide and dimethylformamide; water; or combinations thereof. Of these, preferred solvents are PGME, PGMEA, EL, GBL, HBM, CHO, DAA, or combinations thereof.

[0107] The total solvent content in a photoresist composition (i.e., the cumulative solvent content for all solvents) is typically 40–99% by weight, for example, 60–99% by weight, or 85–99% by weight, based on the total solids content of the photoresist composition. The desired solvent content will depend, for example, on the desired thickness of the photoresist layer to be coated and the coating conditions.

[0108] In some embodiments, the photoresist composition may further comprise a substance containing one or more base-unstable groups ("base-unstable substance"). As referred to herein, a base-unstable group is a functional group that can undergo cleavage reactions in the presence of an aqueous alkaline developer after the exposure step and the post-exposure baking step to provide polar groups such as hydroxyl, carboxylic acid, sulfonic acid, etc. The base-unstable group will not react significantly before the development step of the photoresist composition containing the base-unstable group (e.g., it will not undergo bond cleavage reactions). Therefore, for example, the base-unstable group will be substantially inert during the pre-exposure soft bake, exposure, and post-exposure bake steps. "Substantially inert" means that 5% or less, typically 1% or less, of the base-unstable group (or portion thereof) will decompose, cleave, or react during the pre-exposure soft bake, exposure, and post-exposure bake steps. The base-unstable group reacts well under typical photoresist development conditions using an aqueous alkaline photoresist developer, such as a 0.26 N (N) aqueous solution of tetramethylammonium hydroxide (TMAH). For example, a 0.26 N aqueous solution of TMAH can be used for single-paddle development or dynamic development, in which case the 0.26 N TMAH developer is distributed onto the imaged photoresist layer for a suitable time, such as 10 to 120 seconds (s). Exemplary base-unstable groups are ester groups, typically fluorinated ester groups. Preferably, the base-unstable substance is substantially miscible with the first and / or second polymer and other solid components of the photoresist composition and has a lower surface energy than them. When coated onto a substrate, the base-unstable substance can thereby be separated from the other solid components of the photoresist composition to the top surface of the formed photoresist layer.

[0109] In some embodiments, the base-unstable material may be a polymer material, also referred to herein as a base-unstable polymer, and may comprise one or more repeating units comprising one or more base-unstable groups. For example, a base-unstable polymer may comprise repeating units comprising two or more identical or different base-unstable groups. A preferred base-unstable polymer comprises at least one repeating unit comprising two or more base-unstable groups, for example, a repeating unit comprising two or three base-unstable groups.

[0110] Base-unstable polymers can be prepared using any suitable method in the art, including those described herein for the first and second polymers. For example, base-unstable polymers can be obtained by polymerization of each monomer under any suitable conditions, such as heating at an effective temperature, irradiation with chemical rays at an effective wavelength, or a combination thereof. In addition, or alternatively, one or more base-unstable groups can be grafted onto the polymer backbone using a suitable method.

[0111] In some embodiments, the base-unstable substance is a single molecule comprising one or more base-unstable ester groups, preferably one or more fluorinated ester groups. The base-unstable substance, being a single molecule, typically has a molecular weight in the range of 50 to 1,500 Da. W It holds.

[0112] If present, the base-unstable substance is typically present in the photoresist composition in an amount of 0.01 to 10% by weight or 2 to 7% by weight, typically 1 to 5% by weight, based on the total solid content of the photoresist composition.

[0113] In addition to, or instead of, the base-unstable polymer, the photoresist composition may further include one or more polymers in addition to and different from the non-solvent, alkali-insoluble substrates described above. For example, the photoresist composition may include additional polymers, such as, but with different compositions, as described above. In addition to, or instead of, the one or more additional polymers may include those well known in photoresist technology, such as polyacrylates, polyvinyl ethers, polyesters, polynorbornene, polyacetals, polyethylene glycols, polyamides, polyacrylamides, polyphenols, novolacs, styrene polymers, polyvinyl alcohols, or combinations thereof.

[0114] The photoresist composition may further contain one or more additional, optional additives. For example, optional additives may include chemical laser dyes and contrast agents, striation inhibitors, plasticizers, rate accelerators, sensitizers, photodegradable deactivators (PDQ) (also known as photodegradable bases), basic deactivators, thermoacid generators, surfactants, etc., or combinations thereof. If present, the optional additives are typically present in the photoresist composition in an amount of 0.01 to 10% by weight, based on the total solids content of the photoresist composition.

[0115] PDQ generates a weak acid upon irradiation. The acid generated from the photodegradable deactivator is not strong enough to rapidly react with the acid-unstable groups present in the resist matrix. Exemplary photodegradable deactivators include, for example, photodegradable cations, preferably, for example, C 1~20 Carboxylic acid or C 1~20 This includes compounds useful for preparing strong acid-generating compounds paired with anions of weak acids (pKa>1), such as sulfonic acid anions. Exemplary carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, salicylic acid, etc. Exemplary sulfonic acids include p-toluenesulfonic acid, camphorsulfonic acid, etc. In preferred embodiments, the photodegradable deactivator is a photodegradable organic zwitterionic compound such as diphenyliodonium-2-carboxylate.

[0116] The photodegradable inactivator may be in a non-polymeric form or in a polymer-bound form. When in a polymeric form, the photodegradable inactivator is present in polymerization units on the first or second polymer. Polymerization units containing the photodegradable inactivator are typically present in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, and more preferably 1 to 2 mol%, based on the total repeating units of the polymer.

[0117] Examples of basic deactivators include linear aliphatic amines such as tributylamine, trioctylamine, triisopropanolamine, tetrakis(2-hydroxypropyl)ethylenediamine:N-tert-butyldiethanolamine, tris(2-acetoxyethyl)amine, 2,2',2'',2'''-(ethane-1,2-diyrbis(azantriyl))tetraethanol, 2-(dibutylamino)ethanol, and 2,2',2''-nitrilotriethanol; 1-(tert-butoxycarbonyl)-4-hydroxypiperidine, tert-butyl 1-pyrrolidine carboxylate, tert-butyl 2-ethyl-1H-imidazole-1-carboxylate, and di-tert-butyl Cyclic aliphatic amines such as piperazine-1,4-dicarboxylate and N-(2-acetoxy-ethyl)morpholine; aromatic amines such as pyridine, di-tert-butylpyridine, and pyridinium; N,N-bis(2-hydroxyethyl)pivalamide, N,N-diethylacetamide, N 1 ,N 1 ,N 3 ,N 3This includes linear and cyclic amides and their derivatives such as tetrabutylmalonamide, 1-methylazepan-2-one, 1-allylazepan-2-one, and tert-butyl 1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylcarbamate; ammonium salts such as quaternary ammonium salts of sulfonates, sulfamates, carboxylates, and phosphonates; imines such as primary and secondary aldimines and ketimines; diazines such as optionally substituted pyrazines, piperazines, and phenazines; diazoles such as optionally substituted pyrazoles, thiadiazoles, and imidazoles; and optionally substituted pyrrolidones such as 2-pyrrolidone and cyclohexylpyrrolidine.

[0118] The basic deactivator may be in a non-polymeric form or in a polymer-bound form. When in a polymeric form, the deactivator may be present within the repeating units of the polymer. Repeating units containing the deactivator are typically present in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, and more preferably 1 to 2 mol%, based on the total repeating units of the polymer.

[0119] Exemplary surfactants include fluorinated and non-fluorinated surfactants, and can be ionic or nonionic, with nonionic surfactants being preferred. Exemplary fluorinated nonionic surfactants include perfluoro C4 surfactants such as FC-4430 and FC-4432 surfactants available from 3M Corporation; and fluorodiols such as POLYFOX PF-636, PF-6320, PF-656, and PF-6520 fluorosurfactants from Omnova. In some embodiments, the photoresist composition further comprises a surfactant polymer containing fluorine-containing repeating units.

[0120] A pattern-forming method using the photoresist composition of the present invention is described herein. Suitable substrates on which the photoresist composition can be coated include electronic device substrates. A wide variety of electronic device substrates, such as semiconductor wafers; polycrystalline silicon substrates; packaging substrates such as multi-chip modules; flat panel display substrates; substrates for light-emitting diodes (LEDs), including organic light-emitting diodes (OLEDs), can be used in the present invention, with semiconductor wafers being typical. Such substrates are typically composed of one or more of silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. 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. Such substrates can be of any suitable size. Typical wafer substrate diameters are 200-300 millimeters (mm), but wafers with smaller and larger diameters can be suitably used according to the present invention. The substrate may include one or more layers or structures that optionally contain the effective or operable portion of the device being formed.

[0121] Typically, one or more lithography layers, such as a hard mask layer (e.g., spin-on carbon (SOC), amorphous carbon, or metallic hard mask layer), a CVD layer (e.g., silicon nitride (SiN), silicon oxide (SiO), or silicon oxynitride (SiON) layer), an organic or inorganic underlayer, or a combination thereof, are provided on the upper surface of the substrate before coating with the photoresist composition of the present invention. Such layers, together with the overcoated photoresist layer, form a lithography material stack.

[0122] Optionally, a layer of adhesion promoter may be applied to the substrate surface before coating the photoresist composition. If an adhesion promoter is desired, any suitable adhesion promoter for polymer films may be used, such as silanes, typically organosilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, and hexamethyldisilazane, or aminosilane couplers such as gamma-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those available from DuPont Electronics & Industrial (Marlborough, Massachusetts) under the names AP® 3000, AP® 8000, and AP® 9000S.

[0123] The photoresist composition can be coated onto a substrate by any preferred method, such as spin coating, spray coating, dip coating, doctor blading, etc. For example, the application of a photoresist layer can be achieved by spin coating the photoresist in a solvent using a coating track, in which case the photoresist is distributed onto a rotating wafer. During distribution, the wafer is rotated for 15 to 120 seconds at a speed typically of 4,000 revolutions per minute (rpm) or less, for example, 200 to 3,000 rpm, for example, 1,000 to 2,500 rpm, to obtain a layer of the photoresist composition on the substrate. It will be well understood by those skilled in the art that the thickness of the coated layer can be adjusted by changing the spin speed and / or the total solid content of the composition. The photoresist composition layer formed from the composition of the present invention typically has a dry layer thickness of 1 nanometer (nm) to 120 micrometers (μm), preferably more than 5 nm to 110 μm, more preferably 6 to 100 μm. In some embodiments, the photoresist composition layer formed from this composition may have a dry layer thickness of 10 nm to 5 μm, or 3 to 20 μm.

[0124] The photoresist composition is then typically 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 is performed, for example, on a hot plate or in an oven, with a hot plate being typical. The soft bake temperature and time will depend, for example, on the photoresist composition and thickness. The soft bake temperature is typically 80 - 170 °C, more typically 90 - 150 °C. The soft bake time is typically 10 seconds - 20 minutes, more typically 1 - 10 minutes, and even more typically 1 - 2 minutes. The heating time can be readily determined by one skilled in the art based on the components of the composition.

[0125] The photoresist layer is then patternwise exposed to actinic radiation to create a difference in solubility between the exposed and unexposed regions. The reference herein to exposing the photoresist composition to radiation that activates the composition indicates that the radiation can form a latent image in the photoresist composition. Exposure is typically performed through a patterned photomask having optically transparent and optically opaque regions corresponding, respectively, to the regions of the resist layer that are exposed and not exposed. Such exposure can alternatively be performed without a photomask by direct writing, which is typically used for e-beam lithography. The actinic radiation typically has a wavelength of less than 400 nm, less than 300 nm or less than 200 nm, with 248 nm (KrF), 193 nm (ArF), 13.5 nm (EUV) wavelengths or e-beam lithography being preferred. Preferably, the actinic radiation is 248 nm radiation. This method is used in immersion or dry (non-immersion) lithography techniques. The exposure energy typically ranges from 1 to 200 millijoules per square centimeter (mJ / cm 2 ), preferably 10 - 100 mJ / cm 2 , more preferably 20 - 50 mJ / cm 2 and depends on the exposure tool and the components of the photoresist composition.

[0126] After exposure of the photoresist layer, post-exposure baking (PEB) of the exposed photoresist layer is performed. The PEB can be carried out, for example, on a hot plate or in an oven, and a hot plate is typical. The conditions for the PEB will depend, for example, on the photoresist composition and layer thickness. The PEB is typically performed at a temperature of 70 to 150 °C, preferably 75 to 120 °C, for a time of 30 to 120 seconds. A latent image defined by a region (exposed region) and a non-switched region (non-exposed region) due to polarity switching is formed in the photoresist.

[0127] The exposed photoresist layer is then developed with a suitable developer to selectively remove those regions of the layer that are soluble in the developer, while the remaining insoluble regions form the resulting photoresist pattern relief image. In the case of a positive tone development (PTD) process, the exposed regions of the photoresist layer are removed during development and the non-exposed regions remain. Conversely, in a negative tone development (NTD) process, the exposed regions of the photoresist layer remain and the non-exposed regions are removed during development. The application of the developer can be achieved by any suitable method as described above with respect to the coating of the photoresist composition, and spin coating is typical. The development time is a time effective for removing the soluble regions of the photoresist, and a time of 5 to 60 seconds is typical. The development is typically carried out at room temperature.

[0128] Suitable developers for the PTD process include aqueous base developers, such as tetramethylammonium hydroxide (TMAH), preferably 0.26 N (N) TMAH, quaternary ammonium hydroxide solutions such as tetraethylammonium hydroxide and tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. Suitable developers for the NTD process are organic solvent systems, meaning that the cumulative content of organic solvents in the developer is 50% by weight or more, typically 95% by weight or more, 98% by weight or more, or 100% by weight, based on the total weight of the developer. Suitable organic solvents for NTD developers include, for example, those selected from ketones, esters, ethers, hydrocarbons, and mixtures thereof. The developer is typically 2-heptanone or n-butyl acetate.

[0129] A coated substrate may be formed from the photoresist composition of the present invention. Such a coated substrate comprises (a) a substrate having one or more layers patterned on its surface; and (b) a layer of the photoresist composition on one or more patterned layers.

[0130] A photoresist pattern can be used, for example, as an etch mask, thereby enabling the transfer of the pattern to one or more consecutive underlying layers by known etching techniques, typically dry etching such as reactive ion etching. A photoresist pattern can be used, for example, for pattern transfer to an underlying hard mask layer, and it can subsequently be used as an etch mask for pattern transfer to one or more layers below the hard mask layer. If the photoresist pattern is not consumed during pattern transfer, it can be removed from the substrate by known techniques, such as oxygen plasma ashing. When used in one or more such patterning processes, photoresist compositions can be used to manufacture semiconductor devices such as memory devices, processor chips (CPUs), graphics chips, optoelectronic chips, LEDs, OLEDs, and other electronic devices.

[0131] The present invention is further illustrated by the following non-limiting embodiments. [Examples]

[0132] All reactions were carried out under ambient conditions. All chemicals were used directly from suppliers. Nuclear magnetic resonance (NMR) spectra for all compounds were obtained using a 500 MHz spectrometer unless otherwise specified. Chemical shifts are reported as δ (parts per million, ppm) values ​​relative to the internal deuterated 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).

[0133] Synthesis of sodium 4-carboxy-2-hydroxybenzenesulfonate [ka] Sulfur trioxide-trimethylamine (SO3-TMA) (0.7 g) was added to a solution of 3-hydroxybenzoic acid (20.0 g) in H2SO4 (40 ml) at room temperature. The reaction mixture was heated to 100°C, stirred for 16 hours, cooled to room temperature, and diluted with ice water, and subsequently with 25% aqueous NaOH. The resulting solid was stirred for 30 minutes, filtered, suspended in toluene (40 mL), and distilled. This process was repeated twice, and the solid was then washed with acetone (3 × 50 mL), dried, and obtained sodium 4-carboxy-2-hydroxybenzenesulfonate (25 g, 72%) as a pale green solid. ESI-MS:[M-Na] - :217.13

[0134] Synthesis of 2-hydroxy-4-((2-(methacryloyloxy)ethoxy)carbonyl)benzenesulfonate sodium [ka] Phosgene (3.96 g) in dimethylformamide (DMF) (3.0 mL) was added at 0°C to a solution of sodium 4-carboxy-2-hydroxybenzenesulfonate (3.0 g) in 1,2-dimethoxyethane (60 mL), and the mixture was warmed to room temperature and stirred for 16 hours. The crude mixture was concentrated under an argon atmosphere, followed by the addition of hydroxyethyl methacrylate (15 mL). The reaction mixture was cooled to 0°C, triethylamine (3.78 g) was added, and the reaction mixture was warmed to room temperature and stirred for 24 hours. Ethyl acetate was added, and the organic layer was washed with water, then with brine. The organic layer was concentrated under reduced pressure, and the resulting solid was washed with methyl tert-butyl ether (MTBE). Further purification was achieved by silica gel column chromatography (gradient dichloromethane with 0%-10% methanol) to obtain 2-hydroxy-4-((2-(methacryloyloxy)ethoxy)carbonyl)benzenesulfonate sodium (0.45 g, 10%) as an off-white solid. ESI-MS:[M-Na] - :329.43 1 H NMR(400MHz,DMSO-d6):δ 10.64(s,1H),7.57(d,J=8.0Hz,1H),7.38(dd,J=8.0,1.6Hz,1H),7.29(d,J=1.6Hz,1H) ,6.02(s,1H),5.68(t,J=1.6Hz,1H),4.52-4.49(m,2H),4.45-4.43(m,2H),1.86(s,3H).

[0135] Synthesis of triphenylsulfonium 2-hydroxy-4-((2-(methacryloyloxy)ethoxy)carbonyl)benzenesulfonate (M1) [ka] Triphenylsulfonium bromide (5.8 g) and sodium 2-hydroxy-4-((2-(methacryloyloxy)ethoxy)carbonyl)benzenesulfonate (5.1 g) were dissolved in dichloromethane (116 mL) and water (58 mL). The mixture was vigorously stirred for 4 hours, the organic layer was separated and washed with water (5 × 100 mL), and then the organic layer was concentrated under reduced pressure to obtain triphenylsulfonium 2-hydroxy-4-((2-(methacryloyloxy)ethoxy)carbonyl)benzenesulfonate M1 (6.5 g, 66%) as a thick solid. ESI-MS: ([M] - ):329.22, [M] + :263.27 1 H NMR(400MHz,DMSO-d6):δ 10.65(s,1H),7.88-7.76(m,15H),7.57(d,J=8.0Hz,1H),7.38(dd,J=8.0,1.6Hz,1H),7.29(d,J=1. 6Hz,1H),6.03-6.02(m,1H),5.68-5.67(m,1H),4.52-4.49(m,2H),4.45-4.43(m,2H),1.86(s,3H).

[0136] Synthesis of tetraethylammonium 4-((2,6-diiodo-4-vinylphenoxy)carbonyl)-2-hydroxybenzenesulfonate: [ka] A mixture of 2,6-diiodo-4-vinylphenol (9.03 g, 24.3 mmol), sodium 4-carboxy-2-hydroxybenzenesulfonate (7.00 g, 29.2 mmol), and pyridine (2.35 mL, 29.2 mmol) was dissolved in N,N-dimethylformamide (70 mL). 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride [EDC HCl] (5.59 g, 29.2 mmol) was added in small amounts at room temperature, and the reaction mixture was stirred for 2 hours. The reaction mixture was poured into a solution of tetraethylammonium chloride (12.0 g, 72.7 mmol) in water (100 mL). This solution was extracted with dichloromethane (150 mL x 2). The combined organic layers were washed with water (300 mL x 3). The organic layers were dried on filter paper and concentrated under reduced pressure. The resulting residue was recrystallized at 0°C from acetone / methyl tert-butyl ether. The obtained solid was filtered and thoroughly rinsed with methyl tert-butyl ether. The solid was dried on filter paper under vacuum at room temperature to obtain tetraethylammonium 4-((2,6-diiodo-4-vinylphenoxy)carbonyl)-2-hydroxybenzenesulfonate (9.54 g, 56%). 1 H NMR(500MHz,DMSO-d6)δ 10.77(s,1H),8.05(s,2H),7.72(d,1H),7.64(d,1H),7.53(s,1H),6.69(dd,1H),5.99(d,1H),3.20(q,8H),1.16(m,12H).

[0137] Synthesis of bis(3,5-difluorophenyl)(4-fluorophenyl)sulfonium 4-((2,6-diiodo-4-vinylphenoxy)carbonyl)-2-hydroxybenzenesulfonate (M2) [ka] A mixture of tetraethylammonium 4-((2,6-diiodo-4-vinylphenoxy)carbonyl)-2-hydroxybenzenesulfonate (9.54 g, 13.6 mmol) and bis(3,5-difluorophenyl)(4-fluorophenyl)sulfonium trifluoromethanesulfonate (6.83 g, 13.6 mmol) was partitioned between dichloromethane (100 mL) and water (100 mL). The mixture was stirred at room temperature for 1 hour. The layers were separated and the organic layer was washed with saturated sodium chloride solution (100 mL × 3) and water (100 mL × 3). The organic layer was diluted to 300 mL with dichloromethane and washed with additional saturated sodium chloride solution (300 mL × 2) and water (300 mL × 3). The resulting organic layer was dried over filter paper and concentrated under reduced pressure. The residue was dissolved in acetone (70 mL) and methyl tert-butyl ether (600 mL) was added. The solution was cooled to 0 °C for 1 hour. The precipitated solid was isolated by decantation of the liquid and then dried under vacuum to give 11.5 g of bis(3,5-difluorophenyl)(4-fluorophenyl)sulfonium 4-((2,6-diiodo-4-vinylphenoxy)carbonyl)-2-hydroxybenzenesulfonate (11.5 g, 91%) M2. 1 H NMR (500 MHz, Acetone-d6) δ 10.91 (s, 1H), 8.46 - 8.15 (m, 2H), 8.04 (s, 2H), 7.92 - 7.74 (m, 5H), 7.74 - 7.51 (m, 6H), 6.73 (dd, J = 17.6, 11.0 Hz, 1H), 5.96 (d, J = 17.6 Hz, 1H), 5.39 (d, J = 十一.0 Hz, 1H). 19 F NMR (470 MHz, Acetone) δ -101.9 (m), -103.9 (m).

[0138] Polymer synthesis Polymers P1 - P4 and comparative polymer P5 were prepared using the following monomers.

Chemical formula

[0139] Synthesis of polymer P1 Polymer P1 was prepared from monomers MA1, MB2, and M1 in a molar supply ratio of 40:50:10. The supply solution was prepared by dissolving dimethyl 2,2'-azobis(2-methylpropionate), obtained from Wako Pure Chemical Industries, Ltd., in propylene glycol monomethyl ether (PGME, 30.58 g) with MA1 (4.86 g, 40.5 mmol), MB2 (10.34 g, 50.61 mmol), M1 (6.00 g, 10.12 mmol), and V-601 initiator (2.94 g, 12.65 mmol; obtained from Wako Pure Chemical Industries, Ltd.).

[0140] Polymerization was carried out in a flask equipped with a condenser and a thermometer to monitor the reaction in the flask. 30.0 g of PGMEA was charged into the reactor and heated to 80°C. The feed solution prepared above was supplied to the flask using a syringe pump over 4 hours. After the addition, the contents were stirred for an additional 2 hours. The contents were then cooled to room temperature. The polymer solution was slowly added to a large excess of isopropanol (500 mL) to precipitate the polymer. The resulting polymer precipitate was isolated by filtration and dried. The crude polymer was dissolved in THF to make a 40% solid solution, which was slowly poured into water, and the precipitated polymer P1 was filtered and dried.

[0141] Each of the polymers P2 to P5 in Table 1 was prepared using the same procedure as described for the preparation of polymer P1, except that the monomers and molar supply ratios specified in Table 1 were used. Molecular weight M for each of the polymers P1 to P5 w (As determined by GPC, in Dalton, Da units) and multivariance index (PDI, M w / M n I will report this again.

[0142] [Table 1]

[0143] Evaluation results Photoresist compositions PR-1 to PR-5 were prepared by combining the components shown in Table 2, with a total solids ratio of 90.91% by weight of each polymer and 9.09% by weight of the deactivator Q1. The total solids content for each photoresist composition was 2% by weight. Each mixture was shaken using a mechanical shaker and then filtered through a PTFE disc filter with a pore size of 0.2 microns.

[0144] The evaluation was performed using the CLEAN TRACK ACT8 (TEL, Tokyo Electron Limited) wafer track. A 200 nm wafer for photolithography testing was coated with AR™3 BARC (DuPont Electronics & Industrial) and baked at 205°C for 60 seconds to obtain a 60 nm film. Next, a photoresist composition was coated onto the BARC and soft-baked at 110°C for 60 seconds to obtain a photoresist film layer with a thickness of approximately 50 nm.

[0145] The wafer was exposed to 248nm radiation using a Canon FPA-5000 ES4 scanner (NA=0.8, outer sigma=0.85, inner sigma=0.57) with a mask having a cutout feature.

[0146] Wafers were exposed to light at 100°C for 60 seconds, baked, developed with MF(trademark) CD26 TMAH developer (DuPont Electronics & Industrial) for 60 seconds, rinsed with DI water, and dried. Clearing dose (E0) values ​​were obtained from open-frame energy meandering. Film thickness was measured using a KLA-Tencor Therma-wave OptiProbe ellipsometer. Dose-to-clear was determined by the energy at which the resist film thickness reached 20 Å or less.

[0147] The structures of the deactivator used in the formulation and the PAG-A used in the comparative example were as follows: [ka]

[0148] [Table 2]

[0149] Table 2 demonstrates that all photoresist compositions PR-1 to PR-4, containing the polymer-bound photoacid generator (PAG) of the present invention, exhibit higher dose-to-clear values ​​compared to Comparative Example PR-5, which contains polymer-free PAG and additive PAG-A. These results indicate that the incorporation of PAG into the polymer leads to acid diffusion.

[0150] While this disclosure has been described in relation to what is currently considered to be a practical and exemplary embodiment, it should be understood that the present invention is not limited to the disclosed embodiments, but rather is intended to encompass various modifications and equivalent arrangements that fall within the spirit and scope of the appended claims.

Claims

1. Anions and; Cation and; The polymerizable group bonded to the anion or cation and A polymerizable compound containing, The anion is (i) a monocyclic or polycyclic C containing a first substituent. ３～６０ It contains an aromatic group and (ii) an anionic stabilizing group, The first substituent comprises an anionic group, and the anionic group is selected from a sulfonate anionic group, a sulfinate anionic group, a sulfonimide anionic group, a sulfamate anionic group, or a sulfonamide anionic group. The anion stabilizing group is configured to form an intramolecular non-covalent bond with the anion group, and The first substituent further comprises an anion stabilizing group, or the monocyclic or polycyclic C ３～６０ The aromatic group further comprises a second substituent, the second substituent comprising an anion stabilizing group. Polymerizable compound.

2. The aforementioned anion is given by formula (1): 【Chemistry 1】 (In equation (1), Ar １ This is a monocyclic or polycyclic C ３～６０ It is an aromatic group, Each L １ These are independently single bonds or one or more divalent linking groups, L １ It does not contain fluorine. Each L ２ These are independently single bonds or one or more divalent linking groups. Each R １ These are independently non-hydrogen substituents, Each Z １ independently contains an anion stabilizing group, and at least one Z １ is configured to form a ring having 5 to 8 atoms by forming an intramolecular non-covalent bond with the sulfonate anion group, and Z １ independently is —OH, —C(O)OH, —SH, —C(O)SH, —NHS(O) ２ R ２ , —S(O) ２ R ２ , —S(O) ２ NHS(O) ２ R ２ , —CH(═NOH), or —B(R ３ ) ２ is selected from; each Z １ optionally further contains one or more divalent linking groups as part of its structure, Each R ２ These are, independently, 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, Each R ３ 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 Ar, together, optionally, １ A condensed ring is formed, and the condensed ring optionally further includes one or more divalent linking groups as part of its structure. One Z １ and one R １ Ar, together, optionally, １ A condensed ring is formed, and the condensed ring optionally further includes one or more divalent linking groups as part of its structure. Each of a and b is an independent integer between 0 and 2, provided that 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. P is a polymerizable group. The polymerizable compound according to claim 1.

3. L ２ -O-, -C(O)-, -C(O)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 Heterocycloalkylenes, 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, where each R' is independently hydrogen, substituted or unsubstituted carbon. １～２０ Alkyl, substituted, or unsubstituted C １～２０ Heteroalkyl, substituted, or unsubstituted C ６～３０ Aryl, or substituted or unsubstituted C ３～３０ The polymerizable compound according to claim 2, wherein it is a heteroaryl compound.

4. L １ The polymerizable compound according to claim 2 or 3, wherein the bond is a single bond.

5. The polymerizable compound according to any one of claims 1 to 4, wherein the cation is iodonium or sulfonium.

6. The polymerizable compound according to any one of claims 1 to 5, wherein the cation comprises ammonium.

7. A polymerizable compound according to any one of claims 1 to 6, wherein at least one anionic stabilizing group comprises -OH.

8. Ar １ This is a single ring C ６ A polymerizable compound according to any one of claims 1 to 7, wherein the polymerizable compound is an aromatic group.

9. L ２ The polymerizable compound according to any one of claims 1 to 8, wherein the compound comprises an iodine-substituted aromatic group.

10. A polymerizable compound according to any one of claims 1 to 9; or a polymer comprising repeating units derived from the polymerizable compound according to any one of claims 1 to 9; solvent and A photoresist composition containing [a specific compound / component].

11. The photoresist composition according to claim 10, further comprising a solvent-free alkali-insoluble substrate.

12. A pattern formation method, To provide a photoresist composition layer by coating a layer of the photoresist composition according to claim 10 or 11 onto a substrate; To provide a photoresist composition layer exposed by pattern exposure with activating radiation; The exposed photoresist composition layer is developed to provide a resist relief image. A method that includes this.

Images