Photoresist composition and method of manufacturing integrated circuit device by using same

Abstract

A photoresist composition and a method of manufacturing an integrated circuit device by using the same are provided. The photoresist composition includes a photosensitive polymer and a solvent wherein the photosensitive polymer includes a pyridinium salt and a functional group that is convertible (e.g., convertible) to a radical and bonded to the pyridinium salt, and the radical-convertible functional group includes an oxygen atom, a nitrogen atom, or a carbon atom bonded to a nitrogen atom of the pyridinium salt, and a radical can be generated by decomposition of a bond between the oxygen atom, the nitrogen atom, or the carbon atom of the radical-convertible functional group and the nitrogen atom of the pyridinium salt.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to Korean Patent Application No. 10-2024-0006806, filed with the Korean Intellectual Property Office on January 16, 2024, the entire disclosure of which is incorporated herein by reference. Technical field

[0003] The present inventive concept relates to a photoresist composition and a method of manufacturing an integrated circuit device by using the photoresist composition, and more particularly, to a photoresist composition including a pyridinium salt and a method of manufacturing an integrated circuit device by using the photoresist composition. Background art

[0004] Due to the advancement of electronic technology, integrated circuit devices have been rapidly miniaturized. There is still a need for a lithography process that is advantageous in achieving fine patterns. Summary of the invention

[0005] In one aspect, the present inventive concept provides a photoresist composition capable of providing excellent etching resistance and resolution in a lithography process for manufacturing an integrated circuit device.

[0006] In one aspect, the present inventive concept also provides a method of manufacturing an integrated circuit device, the method capable of improving the dimensional accuracy of a pattern intended to be formed by providing excellent etching resistance and resolution.

[0007] However, the present inventive concept is not limited to the aspects set forth above, and the above and other aspects of the present inventive concept will be clearly understood by those of ordinary skill in the art from the following description.

[0008] According to one aspect of the present inventive concept, there is provided a photoresist composition including a photosensitive polymer and a solvent, wherein the photosensitive polymer includes a pyridinium salt and a functional group capable of being converted (e.g., convertible) into a radical and bonded to the pyridinium salt, and the functional group capable of being converted into a radical includes an oxygen atom, a nitrogen atom, or a carbon atom bonded to a nitrogen atom of the pyridinium salt, and is capable of generating a radical by decomposition of a bond between the oxygen atom, the nitrogen atom, or the carbon atom of the functional group capable of being converted into a radical and the nitrogen atom of the pyridinium salt.

[0009] According to another aspect of the present inventive concept, there is provided a photoresist composition including a photosensitive polymer and a solvent, wherein the photosensitive polymer includes a pyridinium salt and a functional group capable of being converted into a radical and bonded to the pyridinium salt, and the functional group capable of being converted into a radical is included in a main chain of the photosensitive polymer.

[0010] According to another aspect of the inventive concept, there is provided a method of manufacturing an integrated circuit device, the method including: forming a photoresist film on a feature layer by using any one of the photoresist compositions described above; generating radicals from the photosensitive polymer in a first region by exposing the first region, which is part of the photoresist film, to light, and inducing a change in polarity of the photosensitive polymer by converting the pyridinium salt of the photosensitive polymer into a pyridine group; and forming a photoresist pattern including an unexposed region of the photoresist film by removing the exposed first region from the photoresist film by using a developer. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Embodiments will be understood more clearly from the following detailed description in conjunction with the accompanying drawings, in which:

[0012] Figure 1 is a flowchart showing a method of manufacturing an integrated circuit device according to some embodiments; and

[0013] Figures 2A to 2E are cross-sectional views showing a series of processes of a method of manufacturing an integrated circuit device according to some embodiments, respectively. DETAILED DESCRIPTION

[0014] Hereinafter, embodiments of the inventive concept will be described in detail with reference to the accompanying drawings. Like reference numerals denote like components throughout the specification, and repetitive descriptions thereof are omitted.

[0015] In the present disclosure, when a chemical bond is not shown at a position where a chemical bond must be drawn in a formula, this may mean that a hydrogen atom is bonded to the position, unless otherwise defined. In the present disclosure, the "pyridinium salt" described with respect to the photosensitive polymer should be understood as a "pyridinium salt group". For example, "the photosensitive polymer includes a pyridinium salt" should be understood as "the photosensitive polymer includes a pyridinium salt group".

[0016] A photoresist composition according to some embodiments may include a photosensitive polymer and a solvent.

[0017] In some embodiments, the photosensitive polymer may include a pyridinium salt and a functional group that can be converted (e.g., capable of being converted) into radicals, the functional group capable of being converted into radicals being bonded to the pyridinium salt.

[0018] As used herein, the term "radical - convertible functional group" may refer to a substituted or unsubstituted functional group having a linear (straight - chain) structure, a cyclic structure, or a mixed structure thereof and including an oxygen atom, a nitrogen atom, or a carbon atom bonded to the nitrogen atom of the pyridinium salt. As used herein, the term "substituted" means that at least one hydrogen atom bonded to a carbon atom is replaced by a substituent, or at least one carbon atom is replaced by a hetero - element - containing group, unless otherwise defined. The substituents may include, for example, halogen elements, hydroxyl groups, aldehyde groups, carboxyl groups, amino groups, cyano groups, isocyanate groups, thiol groups, sulfonic acid groups or their salts, phosphoric acid groups or their salts, C1 - C30 (e.g., C1 - C20, C1 - C10, or C1 - C6) alkyl, C3 - C30 (e.g., C3 - C20, C3 - C10, or C5 - C7) cycloalkyl, C2 - C30 (e.g., C2 - C20, C2 - C10, or C2 - C6) alkenyl, C1 - C30 (e.g., C1 - C20, C1 - C10, or C1 - C6) alkoxy, C2 - C30 (e.g., C2 - C20, C2 - C10, or C2 - C6) alkenoxy, C2 - C30 (e.g., C2 - C20, C2 - C10, or C2 - C6) alkynyl, C6 - C30 (e.g., C6 - C20, C6 - C12, or C6 - C10) aryl, C6 - C30 (e.g., C6 - C20, C6 - C12, or C6 - C10) aryloxy, C7 - C30 (e.g., C7 - C20, C7 - C13, or C7 - C11) alkaryl, C7 - C30 (e.g., C7 - C20, C7 - C13, or C7 - C11) aralkyl, C7 - C30 (e.g., C7 - C20, C7 - C13, or C7 - C11) alkylaryloxy, or C3 - C30 (e.g., C3 - C20, C3 - C12, C3 - C10, or C3 - C8) heteroaryl. The hetero - element - containing group may also be referred to as a hetero - atom - containing group. The hetero - element - containing group may include, for example, -O -, -C(=O)-O -, -O -C(=O)-, -C(=O)-, -O -C(=O)-O -, -C(=O)-NH -, -NH -, -S -, -S(=O)2 -, or -S(=O)2 -O -. However, the radical - convertible functional group is not limited to the functional groups exemplified above and may include various functional groups capable of generating radicals.

[0019] In this text, for a substituted X group (the X group is a C1-C30 alkyl group, a C5-C30 alkyl group, a C2-C30 alkenyl group, a C5-C30 alkenyl group, a C2-C30 alkynyl group, a C3-C30 cycloalkyl group, a C1-C30 alkoxy group, a C2-C30 acyl group, a C7-C30 alkylbenzenesulfonyl group, a C6-C30 aryl group, a C3-C30 heteroaryl group, or a C7-C30 aralkyl group), preferably, the upper limit of the carbon atoms of the X group can be C20, C15, C14, C12, C10, C8, C7, or C6. For example, the C1-C30 alkyl group can preferably be a C1-C20 alkyl group, a C1-C10 alkyl group, or a C1-C6 alkyl group. The C6-C30 aryl group can preferably be a C6-C20 aryl group, a C6-C12 aryl group, or a C6-C10 aryl group. The C7-C30 alkylbenzenesulfonyl group can preferably be a C7-C20 alkylbenzenesulfonyl group, a C7-C15 alkylbenzenesulfonyl group, or a C7-C10 alkylbenzenesulfonyl group. The C7-C30 in the C7-C30 alkylbenzenesulfonyl group refers to the total number of carbon atoms in the alkylbenzenesulfonyl group. The C3-C30 heteroaryl group can preferably be a C3 (or C6)-C20 heteroaryl group, a C3 (or C6)-C12 heteroaryl group, a C3 (or C6)-C10 heteroaryl group, or a C3 (or C6)-C8 heteroaryl group.

[0020] In some embodiments, the functional group capable of being converted into a radical can generate radicals through the decomposition of the bond between the oxygen atom, nitrogen atom or carbon atom of the functional group capable of being converted into a radical and the nitrogen atom of the pyridinium salt.

[0021] In some embodiments, the photosensitive polymer can include a first repeating unit represented by one of the structures of Formula 1.

[0022] [Formula 1]

[0023]

[0024] In Formula 1, OR 11 can be a functional group capable of being converted into a radical. R 11 can be a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, or a substituted or unsubstituted C7-C30 aralkyl group. X 11- can be a non-metallic element or a compound anion. In this text, the non-metallic element anion is composed of only one non-metallic element. For example, the non-metallic element anion can be a halogen ion such as F - , Cl - , Br - , or I -。The compound anion is different from the non-metal element anion and includes at least two elements. The compound anion may include anions derived from compounds such as organic compounds, and negatively charged atomic groups. For example, X 11- may include 4-methylbenzenesulfonate (OTs), BF4 - , or PF6 - . * represents the binding site.

[0025] In some embodiments, R 11 may be a substituted C5 to C30 alkyl group as follows: at least one hydrogen atom bonded to the carbon atom at the 1, 5, or 6 position is replaced by a secondary or higher (e.g., tertiary) substituent, or the carbon atom at the 1, 5, or 6 position is replaced by a hetero-element-containing group such that a 1,5-hydrogen atom transfer reaction can occur. The substituents may include, for example, secondary amides, tertiary amides, secondary alcohols, tertiary alcohols, secondary alkyl halides, tertiary alkyl halides, secondary amines, tertiary amines, secondary ketimines, secondary aldimines, etc. The substituents may have 2-20, for example 3-18, 4-15, or 5-10 carbon atoms. The hetero-element-containing group may include, for example, -O-, -C(=O)-O-, -O-C(=O)-, -C(=O)-, -O-C(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O)2-, or -S(=O)2-O-.

[0026] In some embodiments, R 11 may be a substituted or unsubstituted C5 to C30 alkenyl group having a double bond between the carbon atom at the 4 position and the carbon atom at the 5 position, between the carbon atom at the 5 position and the carbon atom at the 6 position, or between the carbon atom at the 6 position and the carbon atom at the 7 position such that an intramolecular cyclization reaction can occur.

[0027] For example, the photosensitive polymer may include a first repeating unit represented by the structure shown below.

[0028]

[0029] In the above structure, OTs - represents a 4-methylbenzenesulfonate anion, and * represents the binding site.

[0030] In some embodiments, the photosensitive polymer may include a first repeating unit represented by one of the structures of Formula 1-1.

[0031] [Formula 1-1]

[0032]

[0033] In Formula 1-1, R12 can be hydrogen, a C1-C30 alkyl group, a C2-C30 alkenyl group, a C2-C30 alkynyl group, a C3-C30 cycloalkyl group, a C1-C30 alkoxy group, a C6-C30 aryl group, a C3-C30 heteroaryl group, a C7-C30 aralkyl group, or a phenyl group. X 12- can be a non-metallic element or a compound anion. For example, X 12- can include OTs - , BF4 - , or PF6 - . * represents the binding site.

[0034] In some embodiments, the photosensitive polymer may include a second repeating unit represented by one of the structures of Formula 2.

[0035] [Formula 2]

[0036]

[0037] In Formula 2, NR 21 can be a functional group capable of being converted into a radical. R 21 can be a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C7-C30 aralkyl group, a substituted or unsubstituted C2-C30 acyl group, or a substituted or unsubstituted C7-C30 alkylbenzenesulfonyl group. R 22 can be hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C2-C30 acyl group, a substituted or unsubstituted C7-C30 alkylbenzenesulfonyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C7-C30 aralkyl group, or a substituted or unsubstituted phenyl group. X 21- can be a non-metallic element or a compound anion. For example, X 21- can include OTs - , BF4 - , or PF6 - . * represents the binding site.

[0038] In some embodiments, R 21It can be a substituted C5-C30 alkyl group as follows: at least one hydrogen atom bonded to the carbon atom at the 1, 5, or 6 position is replaced by a secondary or higher (e.g., tertiary) substituent, or the carbon atom at the 1, 5, or 6 position is replaced by a heteroatom-containing group, such that a 1,5-hydrogen transfer reaction can occur. The substituents can include, for example, secondary amides, tertiary amides, secondary alcohols, tertiary alcohols, secondary alkyl halides, tertiary alkyl halides, secondary amines, tertiary amines, secondary ketimines, secondary aldimines, etc. The substituents can have 2-20, for example 3-18, 4-15, or 5-10 carbon atoms. The heteroatom-containing group can include, for example, -O-, -C(=O)-O-, -O-C(=O)-, -C(=O)-, -O-C(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O)2-, or -S(=O)2-O-.

[0039] In some embodiments, R 21 can be a substituted or unsubstituted C5-C30 alkenyl group having a double bond between the carbon atom at the 4 position and the carbon atom at the 5 position, between the carbon atom at the 5 position and the carbon atom at the 6 position, or between the carbon atom at the 6 position and the carbon atom at the 7 position, such that an intramolecular cyclization reaction can occur.

[0040] For example, the photosensitive polymer can include a second repeating unit represented by the structure shown below.

[0041]

[0042] In the above structure, OTs - represents the 4-methylbenzenesulfonate anion, Ts represents 4-methylbenzenesulfonyl, and * represents the binding site.

[0043] In some embodiments, the photosensitive polymer can include a third repeating unit represented by one of the structures of Formula 3.

[0044] [Formula 3]

[0045]

[0046] In Formula 3, CR 31 can be a functional group capable of being converted into a radical. R 31 can be a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C7-C30 aralkyl group, a substituted or unsubstituted C2-C30 acyl group, or a substituted or unsubstituted C7-C30 alkylbenzenesulfonyl group. R 32 and R 33may each independently be hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C2-C30 acyl group, a substituted or unsubstituted C7-C30 alkylbenzenesulfonyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C7-C30 aralkyl group, or a substituted or unsubstituted phenyl group. X 31- may be a non-metallic element or a compound anion. For example, X 31- may include OTs - , BF4 - , or PF6 - . * represents a binding site.

[0047] In some embodiments, R 31 may be a substituted C5-C30 alkyl group as follows: at least one hydrogen atom bonded to the carbon atom at the 1, 5, or 6 position is replaced by a secondary or higher (e.g., tertiary) substituent, or the carbon atom at the 1, 5, or 6 position is replaced by a heteroatom-containing group such that a 1,5-hydrogen transfer reaction can occur. The substituents may include, for example, secondary amides, tertiary amides, secondary alcohols, tertiary alcohols, secondary alkyl halides, tertiary alkyl halides, secondary amines, tertiary amines, secondary ketimines, secondary aldimines, etc. The substituents may have 2-20, for example 3-18, 4-15, or 5-10 carbon atoms. The heteroatom-containing group may include, for example, -O-, -C(=O)-O-, -O-C(=O)-, -C(=O)-, -O-C(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O)2-, or -S(=O)2-O-.

[0048] In some embodiments, R 31 may be a substituted or unsubstituted C5-C30 alkenyl group having a double bond between the carbon atom at the 4 position and the carbon atom at the 5 position, between the carbon atom at the 5 position and the carbon atom at the 6 position, or between the carbon atom at the 6 position and the carbon atom at the 7 position such that an intramolecular cyclization reaction can occur.

[0049] In some embodiments, the photosensitive polymer may include a main chain scission (MCS) structure in its main chain, which forms free radicals to cause the scission of the main chain. In some embodiments, the photosensitive polymer may include a functional group that can be converted into free radicals in its main chain.

[0050] In some embodiments, the photosensitive polymer may include an eleventh repeating unit and a twelfth repeating unit, and each of the eleventh repeating unit and the twelfth repeating unit is represented by one of the structures of Formula 1 above. The eleventh repeating unit and the twelfth repeating unit may each independently include an R selected from the following 11 : substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, and substituted or unsubstituted C7-C30 aralkyl.

[0051] In some embodiments, in the photosensitive polymer, the R of the eleventh repeating unit 11 may be bonded to the binding site of the main chain of the twelfth repeating unit. In this case, the R of the eleventh repeating unit 11 is a corresponding divalent group. In other words, the R of the eleventh repeating unit 11 is substituted or unsubstituted C1-C30 alkylene, substituted or unsubstituted C2-C30 alkenylene, or substituted or unsubstituted C7-C30 aralkylene. For example, the photosensitive polymer may include -[C2H3] n -R 11 -O- structure. For example, "n" is a natural number in the range of 1 to 100.

[0052] In some embodiments, the photosensitive polymer may include an eleventh repeating unit and a twelfth repeating unit, and each of the eleventh repeating unit and the twelfth repeating unit is represented by one of the structures of Formula 1-1 above. The eleventh repeating unit and the twelfth repeating unit may each independently include an R selected from the following 12 : hydrogen, C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C3-C30 cycloalkyl, C1-C30 alkoxy, C6-C30 aryl, C3-C30 heteroaryl, C7-C30 aralkyl, and phenyl.

[0053] In some embodiments, in the photosensitive polymer, the R of the eleventh repeating unit 12 may be bonded to the binding site of the main chain of the twelfth repeating unit. In this case, the R of the eleventh repeating unit 12 is a corresponding divalent group. For example, the photosensitive polymer may include -[C2H3] n -R 12 -O- structure. For example, "n" is a natural number in the range of 1 to 100.

[0054] In some embodiments, the photosensitive polymer may include a fourth repeating unit represented by Formula 4.

[0055] [Formula 4]

[0056]

[0057] In Formula 4, OR 41 and OR 42 can each be a functional group capable of being converted into a free radical. R 41 can be a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C2-C30 alkenylene group, or a substituted or unsubstituted C7-C30 arylalkylene group. R 42 can be a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, or a substituted or unsubstituted C7-C30 arylalkyl group. X 41- and X 42- can be a non-metallic element or a compound anion. For example, X 41- and X 42- can each independently be OTs - , BF4 - , or PF6 - . * represents a binding site.

[0058] In some embodiments, R 41 and R 42 can each independently include functional groups similar to the examples of R 11 in Formula 1 above, except that R 41 becomes the corresponding divalent group. R 41 and R 42 can each independently be a substituted C5-C30 alkyl group as follows: wherein at least one hydrogen atom bonded to the carbon atom at the 1, 5, or 6 position is replaced by a secondary or higher (e.g., tertiary) substituent, or the carbon atom at the 1, 5, or 6 position is replaced by a heteroelement-containing group, or R 41 and / or R 42 can each independently be a substituted or unsubstituted C5-C30 alkenyl group having a double bond between the carbon atom at the 4 position and the carbon atom at the 5 position, between the carbon atom at the 5 position and the carbon atom at the 6 position, or between the carbon atom at the 6 position and the carbon atom at the 7 position. A detailed description of the secondary or higher (e.g., tertiary) substituent can be referred to the description of R 11 in Formula 1 above.

[0059] For example, the photosensitive polymer can include a fourth repeating unit represented by the structure shown below.

[0060]

[0061] In the above structure, * represents a binding site.

[0062] In some embodiments, the photosensitive polymer may include a twenty-first repeating unit and a twenty-second repeating unit, and each of the twenty-first repeating unit and the twenty-second repeating unit is represented by one of the structures of Formula 2 above. The twenty-first repeating unit and the twenty-second repeating unit may each independently include an R selected from the following 21 : a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C7-C30 aralkyl group, a substituted or unsubstituted C2-C30 acyl group, and a substituted or unsubstituted C7-C30 alkylbenzenesulfonyl group.

[0063] In some embodiments, in the photosensitive polymer, the R of the twenty-first repeating unit 22 may be bonded to the binding site of the main chain of the twenty-second repeating unit. In this case, the R of the twenty-first repeating unit 22 is a corresponding divalent group. For example, the photosensitive polymer may include -[C2H3] n -R 22 -N- structure. For example, "n" is a natural number in the range of 1 to 100.

[0064] In some embodiments, the photosensitive polymer may include a fifth repeating unit represented by Formula 5.

[0065] [Formula 5]

[0066]

[0067] In Formula 5, NR 51 and NR 53 may each be a functional group capable of being converted into a free radical. R 51 may be a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C2-C30 alkenylene group, a substituted or unsubstituted C1-C30 alkyleneoxy group, a substituted or unsubstituted C7-C30 aralkylene group, a substituted or unsubstituted C2-C30 acyl group, or a substituted or unsubstituted C7-C30 divalent alkylbenzenesulfonyl group. R 53 may be a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C7-C30 aralkyl group, a substituted or unsubstituted C2-C30 acyl group, or a substituted or unsubstituted C7-C30 alkylbenzenesulfonyl group. R 52 and R 54Each may independently be hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C2-C30 acyl group, a substituted or unsubstituted C7-C30 alkylbenzenesulfonyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C7-C30 aralkyl group, or a substituted or unsubstituted phenyl group. X 51 and X 52 may be a non-metallic element or a compound anion. For example, X 51- and X 52- may each independently be OTs - 、BF4 - 、or PF6 - 。* represents the binding site.

[0068] In some embodiments, R 51 and R 53 may each independently include a functional group similar to the examples of R 21 in Formula 2 above, except that R 51 becomes the corresponding divalent group. R 51 and R 53 may each independently be a substituted C5-C30 alkyl group as follows: wherein at least one hydrogen atom bonded to the carbon atom at the 1, 5, or 6 position is replaced by a secondary or higher (e.g., tertiary) substituent, or the carbon atom at the 1, 5, or 6 position is replaced by a heteroatom-containing group, or R 51 and / or R 53 may each independently be a substituted or unsubstituted C5-C30 alkenyl group having a double bond between the carbon atom at the 4 position and the carbon atom at the 5 position, between the carbon atom at the 5 position and the carbon atom at the 6 position, or between the carbon atom at the 6 position and the carbon atom at the 7 position. A detailed description of the secondary or higher (e.g., tertiary) substituent can be referred to the description of R 21 in Formula 2 above.

[0069] In some embodiments, the photosensitive polymer may include a thirty-first repeating unit and a thirty-second repeating unit, and each of the thirty-first repeating unit and the thirty-second repeating unit is represented by one of the structures of Formula 3 above. The thirty-first repeating unit and the thirty-second repeating unit may each independently include an R selected from the following 31: substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C2-C30 acyl, and substituted or unsubstituted C7-C30 alkylbenzenesulfonyl.

[0070] In some embodiments, in the photosensitive polymer, the R of the thirty-first repeating unit 32 can be bonded to the binding site of the main chain of the thirty-second repeating unit. In this case, the R of the thirty-first repeating unit 32 is a corresponding divalent group. For example, the photosensitive polymer may include -[C2H3] n -R 32 -C- structure. For example, "n" is a natural number in the range of 1 to 100.

[0071] In some embodiments, the photosensitive polymer may include a sixth repeating unit represented by Formula 6.

[0072] [Formula 6]

[0073]

[0074] In Formula 6, CR 61 and CR 64 can each be a functional group capable of being converted into a free radical. R 61 can be substituted or unsubstituted C1-C30 alkylene, substituted or unsubstituted C2-C30 alkenylene, substituted or unsubstituted C1-C30 alkyleneoxy, substituted or unsubstituted C7-C30 aralkylene, substituted or unsubstituted C2-C30 acyl, or substituted or unsubstituted C7-C30 divalent alkylbenzenesulfonyl. R 64 can be substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C2-C30 acyl, or substituted or unsubstituted C7-C30 alkylbenzenesulfonyl. R 62 、R 63 、R 65 、and R 66may each independently be hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C2-C30 acyl group, a substituted or unsubstituted C7-C30 alkylbenzenesulfonyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C7-C30 aralkyl group, or a substituted or unsubstituted phenyl group. X 61- and X 62- may each be a non-metallic element or a compound anion. For example, X 61- and X 62- may each independently be OTs - 、BF4 - 、or PF6 - . * indicates a binding site.

[0075] In some embodiments, R 61 and R 64 may each independently include functional groups similar to the examples of R 31 in Formula 3 above, except that R 61 becomes the corresponding divalent group. R 61 and R 64 may each independently be a substituted C5-C30 alkyl group as follows: at least one hydrogen atom bonded to the carbon atom at the 1, 5, or 6 position is replaced by a secondary or higher (e.g., tertiary) substituent, or the carbon atom at the 1, 5, or 6 position is replaced by a heteroelement-containing group, or R 61 and / or R 64 may each independently be a substituted or unsubstituted C5-C30 alkenyl group having a double bond between the carbon atom at the 4 and 5 positions, between the carbon atom at the 5 and 6 positions, or between the carbon atom at the 6 and 7 positions. A detailed description of the secondary or higher (e.g., tertiary) substituent can be referred to the description of R 31 in Formula 3 above.

[0076] In some embodiments, the photosensitive polymer may include at least one selected from the first repeating unit, the second repeating unit, the third repeating unit, the eleventh repeating unit plus the twelfth repeating unit (e.g., the fourth repeating unit), the twenty-first repeating unit plus the twenty-second repeating unit (e.g., the fifth repeating unit), and the thirty-first repeating unit plus the thirty-second repeating unit (e.g., the sixth repeating unit). For example, the photosensitive polymer may include a combination of the first repeating unit and the second repeating unit, a combination of the first repeating unit and the third repeating unit, a combination of the first repeating unit and the eleventh repeating unit plus the twelfth repeating unit, and the like.

[0077] The solvent included in the photoresist composition may include an organic solvent. The organic solvent may include, but is not limited to, at least one of an ether, an alcohol, a glycol ether, an aromatic hydrocarbon compound, a ketone, and an ester. For example, the organic solvent may include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether, propylene glycol butyl ether acetate, ethanol, propanol, isopropanol, isobutanol, 4-methyl-2-pentanol (methyl isobutyl carbinol: MIBC), hexanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol, heptanone, propylene carbonate, butylene carbonate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, γ-butyrolactone, methyl 2-hydroxyisobutyrate, anisole, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate, or a combination thereof.

[0078] In a photoresist composition according to some embodiments, the solvent may be present in an amount in excess of the amount of the main components such as the photosensitive polymer. In some embodiments, the solvent may be present in an amount of about 70 wt% to about 99.8 wt% based on the total weight of the photoresist composition, or in any range therebetween, but the inventive concept is not limited thereto.

[0079] In some embodiments, the photoresist composition may further include a photoinitiator. The photoinitiator may be configured to generate free radicals by absorbing light. For example, the photoinitiator may include a photo radical generator (PRG) configured to generate free radicals in response to exposure to light. After the photoresist film obtained from the photoresist composition is exposed to light, the photoinitiator in the exposed area of the photoresist film may generate free radicals by absorbing light. The free radicals generated by the photoinitiator may react with the first to sixth, eleventh, twelfth, twenty - first, twenty - second, thirty - first, and thirty - second repeating units of the photosensitive polymer. Thus, when the photoinitiator is included in the photoresist composition according to some embodiments, due to the free radicals generated by the photoinitiator, the free radical chain reaction in the photosensitive polymer described below may occur.

[0080] In the case where the photoinitiator is included in the photoresist composition according to some embodiments, when the photoresist film obtained from the photoresist composition is exposed to light, the photoinitiator may supplement the relatively low reactivity of the photoresist composition, and the light sensitivity in the exposed area of the photoresist film may be adjusted depending on the amount of the photoinitiator. In some embodiments, the photoinitiator may accelerate the free radical chain reaction in the photoresist composition by using free radicals in the exposed area of the photoresist film, thereby causing the photoreaction to proceed only limitedly in the exposed area of the photoresist film.

[0081] When exposed to light selected from one of a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F2 excimer laser (157 nm), and an extreme ultraviolet (EUV) laser (13.5 nm), the PRG may absorb the light and generate free radicals, thereby initiating the free radical chain reaction of the photosensitive polymer included in the photoresist composition according to some embodiments. In some embodiments, the PRG may include an acylphosphine oxide - based compound, an oxime ester - based compound, and the like.

[0082] The acylphosphine oxide - based compound may include, for example, 2,4,6 - trimethylbenzoyl - diphenylphosphine oxide, bis(2,4,6 - trimethylbenzoyl) - phenylphosphine oxide, bis(2,6 - dimethoxybenzoyl) - (2,4,4 - trimethylpentyl)phosphine oxide, and the like.

[0083] The oxime ester-based compounds may include, for example, 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyl)oxime, 1-[4-[4-(carboxyphenyl)thio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, 1-[9-ethyl-6-[2-methyl-4-[1-(2,2-dimethyl-1,3-dioxolan-4-yl)methyloxy]benzoyl]-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, and the like.

[0084] In some embodiments, the PRG may include commercially available products, such as 651, 184, 1173, 2959, 127, 907, 369, 379, TPO, 819, OXE01, OXE02, MBF, or 754 (which is a product model of BASF Co., Ltd.).

[0085] The photoresist composition according to the inventive concept may not include the photoinitiator, or may include a single material selected from the PRGs described above or at least two materials selected from the PRGs described above as the photoinitiator. When the photoinitiator is included in the photoresist composition according to some embodiments, the photoinitiator may be present in an amount of about 0.02 wt% to about 10 wt% based on the total weight of the photoresist composition, or in any range therebetween, but the inventive concept is not limited thereto.

[0086] In some embodiments, when the photoresist composition according to some embodiments includes a PRG as the photoinitiator, the photoresist composition may further include a radical quencher capable of capturing radicals.

[0087] In some embodiments, the radical quencher may include a quinone-type radical or a nitroxide (IUPAC name: aminooxy) radical.

[0088] The quinone-type free radicals may include, but are not limited to, p-benzoquinone, hydroquinone (1,4-dihydroxybenzene), hydroquinone monomethyl ether (4-methoxyphenol), hydroquinone monoethyl ether, hydroquinone monophenyl ether, monoterbutylhydroquinone (MTBHQ), ditertbutylhydroquinone, di-tert-amylhydroquinone, methylhydroquinone, p-benzoquinone dioxime, 2,6-dichloro-1,4-benzoquinone, 2,3,5,6-tetramethyl-1,4-benzoquinone, 2,5-dichloro-3,6-dihydroxy-p-benzoquinone, methyl-p-benzoquinone, 6-anilinoquinoline-5,8-quinone, pyrroloquinoline quinone, 2-allyl-6-methoxybenzene-1,4-quinone, or a combination thereof.

[0089] The nitroxide free radicals may include, but are not limited to, ditertbutyl nitroxide (DTBN), 2,2,6,6-tetramethyl-1-piperidine 1-oxyl (TEMPO), oxo-TEMPO (4-oxo-2,2,6,6-tetramethyl-1-piperidine 1-oxyl), 1,1,3,3-tetraethylisoindoline-N-oxyl, N-tert-butyl-N-[1-(diethoxyphosphoryl)-2,2-dimethylpropyl]aminooxy (SG1), N-tert-butyl-N-(2-methyl-1-phenylpropyl)aminooxy (TIPNO), or a combination thereof.

[0090] In some embodiments, the photoresist composition according to some embodiments may further include at least one selected from a leveling agent, a surfactant, a dispersant, a moisture absorbent, and a coupling agent.

[0091] The leveling agent is used to improve the coating flatness when the photoresist composition is coated on a substrate, and commercially available leveling agents known in the art can be used.

[0092] The surfactant can improve the coating uniformity and wettability of the photoresist composition. In some embodiments, the surfactant may include, but is not limited to, sulfate salts, sulfonate salts, phosphate salts, soaps, amine salts, quaternary ammonium salts, polyethylene glycols, alkylphenol ethylene oxide adducts, polyols, nitrogen-containing vinyl polymers, or a combination thereof. For example, the surfactant may include alkylbenzenesulfonates, alkylpyridinium salts, polyethylene glycols, or quaternary ammonium salts. When the photoresist composition includes the surfactant, the surfactant may be present in an amount of about 0.001 wt% to about 3 wt% based on the total weight of the photoresist composition, or any range therein.

[0093] The dispersant can uniformly disperse the corresponding components constituting the photoresist composition in the photoresist composition. In some embodiments, the dispersant may include, but is not limited to, epoxy resin, polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, glucose, sodium dodecyl sulfate, sodium citrate, oleic acid, linoleic acid, or a combination thereof. When the photoresist composition includes the dispersant, the dispersant may be present in an amount of about 0.001 wt% to about 5 wt% based on the total weight of the photoresist composition, or any range therein.

[0094] The moisture absorbent can prevent adverse effects caused by water in the photoresist composition. In some embodiments, the moisture absorbent may include, but is not limited to, polyoxyethylene nonylphenol ether, polyethylene glycol, polypropylene glycol, polyacrylamide, or a combination thereof. When the photoresist composition includes the moisture absorbent, the moisture absorbent may be present in an amount of about 0.001 wt% to about 10 wt% based on the total weight of the photoresist composition, or any range therein.

[0095] The coupling agent can improve the adhesion to the feature layer or the underlying film when the photoresist composition is coated on the feature layer or the underlying film. In some embodiments, the coupling agent may include a silane coupling agent. The silane coupling agent may include, but is not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β - methoxyethoxy)silane, 3 - methacryloxypropyltrimethoxysilane, 3 - acryloxypropyltrimethoxysilane, p - styryltrimethoxysilane, 3 - methacryloxypropylmethyldimethoxysilane, 3 - methacryloxypropylmethyldiethoxysilane, or trimethoxy[3 - (phenylamino)propyl]silane. When the photoresist composition includes the coupling agent, the coupling agent may be present in an amount of about 0.001 wt% to about 5 wt% based on the total weight of the photoresist composition, or any range therein.

[0096] When the photoresist film obtained from the photoresist composition including the photosensitive polymer according to some embodiments is exposed to light, the photoresist composition can absorb light, and the functional group capable of being converted into a free radical can dissociate from the pyridinium salt of the photosensitive polymer. Therefore, in some embodiments, the pyridinium salt of the photosensitive polymer can be converted into a pyridine group and thus be replaced by the pyridine group, and a change in the polarity of the photosensitive polymer can be caused.

[0097] The process of generating radicals by the functional groups that can be converted (e.g., are capable of being converted) into radicals can be described as follows. Secondary electrons can be generated by exposing the photoresist film to light, and the N-O bond in the -N-OR in the first repeating unit in the photosensitive polymer of the photoresist film exposed to light, the N-N bond in the -N-N(R 11 )(R 21 )(R 22 ) in the second repeating unit, or the N-C bond in the -N-C(R 31 )(R 32 )(R 33 ) in the third repeating unit can be decomposed due to the secondary electrons. Alternatively, radicals can be generated by the photoinitiator of the photoresist composition, and the N-O bond in the -N-OR in the first repeating unit in the photosensitive polymer of the photoresist film exposed to light, the N-N bond in the -N-N(R 11 )(R 21 )(R 22 ) in the second repeating unit, or the N-C bond in the -N-C(R 31 )(R 32 )(R 33 ) in the third repeating unit can be decomposed due to the radicals.

[0098] In some embodiments, due to the decomposition of the N-O bond in the -N-OR in the first repeating unit, the N-N bond in the -N-N(R 11 )(R 21 )(R 22 ) in the second repeating unit, or the N-C bond in the -N-C(R 31 )(R 32 )(R 33 ) in the third repeating unit, radicals each having an unpaired electron can be generated. For example, the decomposition of the N-O bond in the -N-OR in the first repeating unit can generate radicals including HO-R 11 ·, the decomposition of the N-N bond in the -N-N(R 11 )(R 21 )(R 22 ) in the second repeating unit can generate radicals including HN-R 21 (R 22 )●, and the decomposition of the N-C bond in the -N-C(R 31 )(R 32 )(R 33 ) in the third repeating unit can generate radicals including HC-R 31 (R 32 )(R 33) ● free radicals. As used herein, the symbol "●" refers to an unpaired electron. Here, when R 11 , R 21 , or R 31 includes a functional group capable of undergoing a 1,5-hydrogen atom transfer reaction or an intramolecular cyclization reaction, free radicals can be generated by the cleavage of the bond between the oxygen atom, nitrogen atom, or carbon atom of the functional group that can be converted into a free radical and the nitrogen atom of the pyridinium salt.

[0099] Then, near the first repeating unit, the second repeating unit, or the third repeating unit from which the functional group that can be converted into a free radical dissociates, the free radical can bond to the ortho position of the pyridinium salt included in the first repeating unit, the second repeating unit, or the third repeating unit to which the functional group that can be converted into a free radical is bonded, and due to the bonding of the free radical, the functional group that can be converted into a free radical can dissociate from the pyridinium salt to generate a new free radical. Therefore, in some embodiments, a series of decomposition reactions of the photosensitive polymer can occur.

[0100] For example, in some embodiments, HO-R 11 · can bond to the ortho position of the pyridinium salt of the first repeating unit to cleave the N-O bond of -N-OR 11 , thereby generating a free radical including HO-R 11 · again, HN-R 21 (R 22 )· can bond to the ortho position of the pyridinium salt of the second repeating unit to cleave the N-N bond of -N-N(R 21 )(R 22 ), thereby generating a free radical including HN-R 21 (R 22 )· again, and HC-R 31 (R 32 )(R 33 )· can bond to the ortho position of the pyridinium salt of the third repeating unit to cleave the N-C bond of -N-C(R 31 )(R 32 )(R 33 ), thereby generating a group including HC-R 31 (R 32 )(R 33 )· again. Therefore, in some embodiments, the N-O bond of -N-OR 11 in the first repeating unit, the N-N bond of -N-N(R 21 )(R 22 ) in the second repeating unit, or the N-C bond of -N-C(R 31 )(R32 )(R 33 ) A series of decomposition reactions of the N-C bond.

[0101] For example, in some embodiments, when a photoresist film obtained from a photoresist composition containing a photosensitive polymer including one of the structures of Formula 1 above is exposed to light, the -N-OR in the first repeating unit 11 A series of decomposition reactions of the N-O bond can be represented by Reaction Scheme 1 shown below.

[0102] [Reaction Scheme 1]

[0103]

[0104] In some embodiments, due to a series of decomposition reactions of free radicals in the photosensitive polymer, the first repeating unit in the photosensitive polymer can be converted from a structure including a pyridinium salt to a structure in which -R 11 OH is bonded to the ortho position of the pyridine group, converted to a structure in which a material selected from PRG added by the photoinitiator is bonded to the ortho position of the pyridine group, or converted to a structure including a pyridine group. In addition, the second repeating unit can be converted from a structure including a pyridinium salt to a structure in which -R 21 -N(R 22 )(H) is bonded to the ortho position of the pyridine group, converted to a structure in which a material selected from PRG added by the photoinitiator is bonded to the ortho position of the pyridine group, or converted to a structure including a pyridine group. In addition, the third repeating unit can be converted from a structure including a pyridinium salt to a structure in which -R 31 C(R 32 )(R 33 )) is bonded to the ortho position of the pyridine group, converted to a structure in which a material selected from PRG added by the photoinitiator is bonded to the ortho position of the pyridine group, or converted to a structure including a pyridine group.

[0105] For example, in some embodiments, when a photoresist film obtained from a photoresist composition containing a photosensitive polymer including one of the structures of Formula 1 above is exposed to light, the reaction in Reaction Scheme 2 shown below can occur, and the first repeating unit in Formula 1 can be converted to a structure including the structure shown as the product of Reaction Scheme 2.

[0106] [Reaction Scheme 2]

[0107]

[0108] In Reaction Scheme 2, R 13 can be, for example, a material selected from the above PRG as a photoinitiator.

[0109] For example, in some embodiments, when a photoresist film obtained from a photoresist composition containing a photosensitive polymer including one of the structures of Formula 2 above is exposed to light, the reaction shown in Reaction Formula 3 below may occur, and the second repeating unit in Formula 2 may be converted into a structure shown as the product of Reaction Formula 3.

[0110] [Reaction Formula 3]

[0111]

[0112] In Reaction Formula 3, R 23 may be, for example, a material selected as a photoinitiator from the above-mentioned PRG.

[0113] The photoresist composition according to some embodiments may include a photosensitive polymer including a functional group capable of being converted into a free radical. During the exposure process, a series of decomposition reactions of the photosensitive polymer may be caused by the decomposition reaction of the photosensitive polymer and the free radicals generated due to the decomposition reaction of the photosensitive polymer and optionally the free radicals generated by the photoinitiator. Although the photosensitive polymer includes a pyridinium salt, since the pyridinium salt of the photosensitive polymer is replaced by a pyridine group due to the dissociation of the functional group capable of being converted into a free radical, the photosensitive polymer may be converted to be soluble in a developer.

[0114] Here, in some embodiments, due to the high reactivity and short lifetime of free radicals, since the photosensitive polymer in the non-exposed area may undergo a relatively small number of decomposition reactions that can be caused by the free radicals penetrating the non-exposed area, the exposure sensitivity in the exposed area of the photoresist film can be improved. Therefore, in some embodiments, excellent resolution and improved sensitivity can be provided in the lithography process, and the critical dimension (CD) distribution of the pattern obtained through the lithography process can be prevented from deteriorating, thereby improving the dimensional accuracy of the intended pattern.

[0115] Alternatively, in some embodiments, when the photoresist film is exposed to light, when the photosensitive polymer includes at least one of the fourth to sixth repeating units, the N-O bond of -N-OR 41 - in the fourth repeating unit, the N-N bond of -N-N(R 51 )(R 52 )- in the fifth repeating unit, or the N-C bond of -N-C(R 61 )(R 62 )(R 63 )- in the sixth repeating unit may be decomposed.

[0116] An exemplary process in which the free-radical convertible functional group dissociates from the pyridinium salt of the photosensitive polymer and radicals are generated from the free-radical convertible functional group, thereby decomposing the main chain of the photosensitive polymer can be described as follows. In some embodiments, secondary electrons can be generated by exposing the photoresist film to light, and the N—O bond of —N—OR in the fourth repeating unit in the photosensitive polymer of the photoresist film exposed to light 41 the N—N bond of —N—N(R 51 )(R 52 )— in the fifth repeating unit, or the N—C bond of —N—C(R 61 )(R 62 )(R 63 )— in the sixth repeating unit can be decomposed due to the secondary electrons. Alternatively, radicals can be generated by the photoinitiator of the photoresist composition, and the N—O bond of —N—OR in the fourth repeating unit in the photosensitive polymer of the photoresist film exposed to light 41 the N—N bond of —N—N(R 51 )(R 52 )— in the fifth repeating unit, or the N—C bond of —N—C(R 61 )(R 62 )(R 63 )— in the sixth repeating unit can be decomposed due to the radicals.

[0117] For example, in some embodiments, when a photoresist film obtained from a photoresist composition comprising a photosensitive polymer including the structure of Formula 4 above is exposed to light, the reaction in Reaction Formula 4 shown below can occur, and the fourth repeating unit in Formula 4 can be converted into a structure shown as the product of Reaction Formula 4.

[0118] [Reaction Formula 4]

[0119]

[0120] In Reaction Formula 4, R 43 can be, for example, a material selected as the photoinitiator from the above PRG.

[0121] When a photoresist composition according to some embodiments includes a photosensitive polymer having an MCS structure, since the main chain of the photosensitive polymer is cleaved by an exposure process, the molecular weight of the photosensitive polymer can be reduced, and thus, the exposure sensitivity in the exposed area of the photoresist film can be improved. Accordingly, in some embodiments, excellent resolution and improved sensitivity can be provided in a lithography process, and deterioration of the CD distribution of a pattern obtained through the lithography process can be prevented, thereby improving the dimensional accuracy of a pattern intended to be formed.

[0122] The photosensitive polymer included in the photoresist composition according to some embodiments can be synthesized by the synthesis method described below. However, the synthesis method of the photosensitive polymer described below is only an example, and the photosensitive polymer can be synthesized by various synthesis methods.

[0123] In some embodiments, a photosensitive polymer including the first repeating unit can be synthesized by a reaction in Synthesis Scheme 1 shown below.

[0124] [Synthesis Scheme 1]

[0125]

[0126] Referring to Synthesis Scheme 1, in some embodiments, poly(4-vinylpyridine) can be synthesized by a polymerization reaction of 4-vinylpyridine (i.e., 4-vinylpyridine), and then, an oxidation reaction of poly(4-vinylpyridine) and an adduct reaction of R 11 -OTs can be sequentially carried out in the stated order, thereby synthesizing a photosensitive polymer including the first repeating unit. In some embodiments, a photosensitive polymer including the first repeating unit can be synthesized by using 4-vinylpyridine-N-oxide as a monomer and adding R 11 -OTs.

[0127] In some embodiments, a photosensitive polymer including the second repeating unit can be synthesized by a reaction in Synthesis Scheme 2 shown below.

[0128] [Synthesis Scheme 2]

[0129]

[0130] In Synthesis Scheme 2, A can be a non-metallic element or a compound anion. In some embodiments, poly(4-vinylpyridine) can be synthesized by a polymerization reaction of 4-vinylpyridine (i.e., 4-vinylpyridine), and then, NH2-A (where A is a non-metallic element or a compound anion), both TsCl and a base, and R 21OTs, thereby synthesizing a photosensitive polymer including the second repeating unit. In some embodiments, the photosensitive polymer including the second repeating unit can be synthesized by using NH2-C5H4N-CH=CH2 as a monomer and sequentially adding both TsCl and a base in the stated order, and R 21 OTs, or by using Ts-N-C5H4N-CH=CH2 as a monomer and adding R 21 OTs for synthesis.

[0131] In some embodiments, the photosensitive polymer including the third repeating unit can be synthesized by a reaction in Synthesis Formula 3 shown below.

[0132] [Synthesis Formula 3]

[0133]

[0134] In Synthesis Formula 3, B can be a non-metallic element or a compound anion. In some embodiments, poly(4-vinylpyridine) can be synthesized by a polymerization reaction of 4-vinylpyridine (i.e., 4-vinylpyridine), and then, an alkylation reaction and an anion exchange reaction can be sequentially carried out in the stated order, thereby synthesizing a photosensitive polymer including the third repeating unit. Alternatively, in some embodiments, the photosensitive polymer including the third repeating unit can be synthesized by using R 31 -CH2-C5H4N-CH=CH2 as a monomer and carrying out an anion exchange reaction.

[0135] In some embodiments, the photosensitive polymer including the fourth repeating unit can be synthesized by a reaction in Synthesis Formula 4 shown below.

[0136] [Synthesis Formula 4]

[0137]

[0138] As shown in Synthesis Formula 4, in some embodiments, [CH2C5H4NO] n -R 41 -O-Ts can be heated, for example, to 80 °C to 90 °C, and then R 42 -OTs is added, thereby synthesizing a photosensitive polymer including the fourth repeating unit.

[0139] Next, a method of manufacturing an integrated circuit device by using a photoresist composition according to some embodiments is described by way of specific examples.

[0140] Figure 1 FIG. is a flowchart showing a method of manufacturing an integrated circuit device according to some embodiments. Figures 2A to 2ECross-sectional views showing a series of processes of a method of manufacturing an integrated circuit device according to some embodiments, respectively.

[0141] Referring to Figure 1 and Figure 2A , in process P10, a feature layer 110 may be formed on a substrate 100. Subsequently, in process P20, a photoresist film 130 may be formed on the feature layer 110 by using a photoresist composition according to some embodiments. The detailed configuration of the photoresist composition is the same as that described above.

[0142] The substrate 100 may include a semiconductor substrate. The feature layer 110 may include an insulating film, a conductive film, or a semiconductor film. For example, the feature layer 110 may include, but is not limited to, a metal, an alloy, a metal carbide, a nitride (e.g., a metal nitride), an oxynitride (e.g., a metal oxynitride), a metal carbon oxide, a semiconductor, polysilicon, an oxide, or a combination thereof.

[0143] In some embodiments, as shown in Figure 2A , before forming the photoresist film 130 on the feature layer 110, a lower film 120 may be formed on the feature layer 110. In this case, the photoresist film 130 may be formed on the lower film 120. The lower film 120 may prevent the photoresist film 130 from being adversely affected by the feature layer 110 under the photoresist film 130. In some embodiments, the lower film 120 may include an organic or inorganic antireflection coating (ARC) material for a KrF excimer laser, an ArF excimer laser, an EUV laser, or any other light source. In some embodiments, the lower film 120 may include a bottom antireflection coating (BARC) film or a developable bottom antireflection coating (DBARC) film. In some embodiments, the lower film 120 may include an organic component having a light absorption structure. The light absorption structure may include, for example, a hydrocarbon compound having a structure in which one or more benzene rings are fused. The lower film 120 may have a thickness of, but is not limited to, about 1 nm to about 100 nm. In some embodiments, the lower film 120 may be omitted.

[0144] To form the photoresist film 130, a photoresist composition according to some embodiments may be coated on the lower film 120 and then heat-treated. The coating may be performed by methods such as spin coating, spray coating, dip coating, etc. The process of heat-treating the photoresist composition may be performed at a temperature of about 80°C to about 300°C for about 10 seconds to about 100 seconds, but the inventive concept is not limited thereto. The thickness of the photoresist film 130 may be dozens to hundreds of times the thickness of the lower film 120. The photoresist film 130 may have a thickness of, but is not limited to, about 10 nm to about 1 μm.

[0145] Referring toFigure 1 and Figure 2B In process P30, a first region 132 that is part of the photoresist film 130 can be exposed to light. As a result, in the photosensitive polymer included in the photoresist film 130 in the first region 132, the radical generation reaction and decomposition reaction of the photosensitive polymer as described above can be caused.

[0146] For example, when the first region 132 that is part of the photoresist film 130 is exposed to light according to Figure 1 process P30, radicals can be generated in the first region 132 by a functional group of a pyridinium salt that can be converted into a radical and bonded to the photosensitive polymer, and the functional group that can be converted into a radical can dissociate from the pyridinium salt of the photosensitive polymer. As a result, the pyridinium salt of the photosensitive polymer can be replaced by a pyridine group, and a change in the polarity of the photosensitive polymer can be caused. Since a second region 134 that is part of the photoresist film 130 is not exposed to light, the photosensitive polymer in the second region 134 can be maintained in a structure including the pyridinium salt. Therefore, the difference in solubility in a developer between the first region 132 and the second region 134 of the photoresist film 130 can be increased.

[0147] Due to the high reactivity and short lifetime of the radicals generated by the dissociation of the functional group of the photosensitive polymer that can be converted into a radical, the photosensitive polymer in the non-exposed region can undergo a relatively small number of decomposition reactions that can be caused by the radicals penetrating into the non-exposed region. Therefore, the exposure sensitivity in the exposed region of the photoresist film 130 can be improved. Accordingly, excellent resolution and improved sensitivity can be provided in a lithography process, and the CD distribution of the pattern obtained by the lithography process can be prevented from deteriorating, thereby improving the dimensional accuracy of the intended pattern.

[0148] In some embodiments, in a case where a photoinitiator is included in the photoresist film 130, when the first region 132 that is part of the photoresist film 130 is exposed to light according to Figure 1 process P30, radicals can be generated by the photoinitiator in the first region 132. The photoinitiator can include a PRG configured to generate radicals in response to light. Therefore, when the first region 132 of the photoresist film 130 is exposed to light according to Figure 1 process P30, the photoinitiator of the photoresist film 130 in the first region 132 can generate radicals by absorbing light, which causes the dissociation of the functional group of the photosensitive polymer that can be converted into a radical from the pyridinium salt of the photosensitive polymer, such that the pyridinium salt is converted into a pyridine group.

[0149] In some embodiments, in order to expose the first region 132 of the photoresist film 130 to light, a photomask 140 having a plurality of light-shielding regions LS and a plurality of light-transmitting regions LT may be aligned at a certain position above the photoresist film 130, and the first region 132 of the photoresist film 130 may be exposed to light through the plurality of light-transmitting regions LT of the photomask 140. To expose the first region 132 of the photoresist film 130 to light, a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F2 excimer laser (157 nm), or an EUV laser (13.5 nm) may be used.

[0150] In some embodiments, the photomask 140 may include a transparent substrate 142 and a plurality of light-shielding patterns 144 in the plurality of light-shielding regions LS formed on the transparent substrate 142. In some embodiments, the transparent substrate 142 may include quartz. In some embodiments, the plurality of light-shielding patterns 144 may include chromium (Cr). The plurality of light-transmitting regions LT may be defined by the plurality of light-shielding patterns 144. According to some embodiments of the inventive concept, in order to expose the first region 132 of the photoresist film 130 to light, a reflective photomask (not shown) for EUV exposure may be used instead of the photomask 140.

[0151] Next, a baking process may be performed by applying heat to the photoresist film 130 including the first region 132 exposed to light.

[0152] The baking process may be performed at a temperature of about 50°C to about 400°C, or within any range thereof, for about 10 seconds to about 150 seconds, or within any range thereof. For example, the baking process may be performed at a temperature of about 150°C to about 250°C for about 60 seconds to about 120 seconds, but the inventive concept is not limited thereto. In some embodiments, depending on the process, the baking process may be omitted.

[0153] Refer to Figure 1 and Figure 2C , in process P40, the first region 132 of the photoresist film 130 may be removed by developing the photoresist film 130 using a developer. As a result, a photoresist pattern 130P including the second region 134 of the photoresist film 130 not exposed to light may be formed.

[0154] The photoresist pattern 130P may include a plurality of openings OP. After forming the photoresist pattern 130P, a lower pattern 120P may be formed by removing a portion of the lower film 120 exposed by the plurality of openings OP.

[0155] In some embodiments, the development of the photoresist film 130 may be performed by a positive tone development (PTD) process.

[0156] In some embodiments, to develop the photoresist film 130, a developer including an organic solvent may be used. For example, the developer may include, but is not limited to, ketones such as methyl ethyl ketone, acetone, cyclohexanone, and 2-heptanone; alcohols such as 4-methyl-2-pentanol, 1-butanol, isopropyl alcohol, 1-propanol, and methanol; esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, and butyrolactone; aromatic compounds such as benzene, xylene, and toluene; or combinations thereof. In some embodiments, an alkaline developer may be used to develop the photoresist film 130. In some embodiments, the alkaline developer may include an aqueous solution of tetramethylammonium hydroxide (TMAH), which may include, for example, 2.38 wt% of TMAH.

[0157] As described with reference to Figure 2B , since the difference in solubility in the developer between the exposed first region 132 and the unexposed second region 134 in the photoresist film 130 increases, when the first region 132 is removed by developing the photoresist film 130, the second region 134 may remain intact without being removed. Thus, after developing the photoresist film 130, residual defects such as footing phenomena may not occur, and a vertical sidewall profile of the photoresist pattern 130P may be obtained. In this way, by improving the sidewall profile of the photoresist pattern 130P, in some embodiments, when processing the feature layer 110 by using the photoresist pattern 130P, the CD of the intended processing region in the feature layer 110 may be precisely controlled.

[0158] In some embodiments, after forming the photoresist pattern 130P by developing the photoresist film 130, a process of hard baking the obtained product may be further performed. Through the hard baking process, unnecessary materials such as the developer remaining on the obtained product in which the photoresist pattern 130P is formed may be removed.

[0159] The hard baking process may be performed at a temperature of about 50°C to about 400°C, or any range therein, for about 10 seconds to about 150 seconds, or any range therein. For example, the hard baking process may be performed at a temperature of about 150°C to about 250°C, or any range therein, for about 60 seconds to about 120 seconds, or any range therein, but the inventive concept is not limited thereto.

[0160] Referring to Figure 1 and Figure 2D , in process P50, in the Figure 2C obtained product, the feature layer 110 may be processed by using the photoresist pattern 130P.

[0161] To process the feature layer 110, various processes may be performed, such as a process of etching the feature layer 110 exposed through the opening OP of the photoresist pattern 130P, a process of injecting impurity ions into the feature layer 110, a process of forming an additional film on the feature layer 110 through the opening OP, and a process of modifying a part of the feature layer 110 through the opening OP. Although Figure 2D an example of forming the feature pattern 110P by etching the feature layer 110 exposed through the opening OP is shown as an example of the process of processing the feature layer 110, the inventive concept is not limited thereto.

[0162] In some embodiments, the process of forming the feature layer 110 may be omitted from the process described with reference to Figure 2A and, in this case, instead of Figure 1 process P50 and the process described with reference to Figure 2D , the substrate 100 may be processed by using the photoresist pattern 130P. For example, various processes may be performed, such as a process of etching a part of the substrate 100 by using the photoresist pattern 130P, a process of injecting impurity ions into a part of the substrate 100, a process of forming an additional film on the substrate 100 through the opening OP, and a process of modifying a part of the substrate 100 through the opening OP.

[0163] With reference to Figure 2E , in the Figure 2D resultant product, the photoresist pattern 130P and the lower pattern 120P remaining on the feature pattern 110P may be removed. To remove the photoresist pattern 130P and the lower pattern 120P, ashing and stripping processes may be used.

[0164] According to the method of manufacturing an integrated circuit device described with reference to Figure 1 and FIGS. 2A to 2E, the difference in solubility in a developer between the exposed area and the non-exposed area of the photoresist film 130 obtained by using the photoresist composition according to the inventive concept may increase, and the CD distribution in the photoresist pattern 130P may be improved. Therefore, when subsequent processes are performed on the feature layer 110 and / or the substrate 100 by using the photoresist pattern 130P, the CD of the processing area or pattern intended to be formed in the feature layer 110 and / or the substrate 100 may be precisely controlled, thereby improving the dimensional accuracy. In addition, the CD distribution of the pattern intended to be formed on the substrate 100 may be uniformly controlled, and the productivity of the manufacturing process of the integrated circuit device may be improved.

[0165] Although the inventive concept has been specifically shown and described with reference to embodiments thereof, it will be understood that various changes in form and detail may be made therein without departing from the spirit and scope of the appended claims.

Claims

1. A photoresist composition, comprising: a photosensitive polymer; and a solvent, wherein the photosensitive polymer comprises a pyridinium salt and a functional group that can be converted into a free radical and is bonded to the pyridinium salt, and the functional group that can be converted into a free radical comprises an oxygen atom, a nitrogen atom, or a carbon atom bonded to the nitrogen atom of the pyridinium salt, and is capable of generating the free radical through the decomposition of a bond between the oxygen atom, nitrogen atom, or carbon atom of the functional group that can be converted into a free radical and the nitrogen atom of the pyridinium salt.

2. The photoresist composition according to claim 1, wherein the photosensitive polymer comprises a first repeating unit represented by one of the structures of Formula 1: [Formula 1] Among them, In Formula 1, R 11 is a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, or a substituted or unsubstituted C7-C30 aralkyl group, X 11- is a non-metallic element or a compound anion, and * represents a binding site.

3. The photoresist composition according to claim 2, wherein R 11 is a substituted C5 to C30 alkyl group as follows: at least one hydrogen atom bonded to the carbon atom at the 1, 5, or 6 position is replaced by a secondary or tertiary substituent, or the carbon atom at the 1, 5, or 6 position is replaced by a heteroelement-containing group.

4. The photoresist composition according to claim 2, wherein R 11 is a substituted or unsubstituted C5-C30 alkenyl group having a double bond between the carbon atom at the 4-position and the carbon atom at the 5-position, between the carbon atom at the 5-position and the carbon atom at the 6-position, or between the carbon atom at the 6-position and the carbon atom at the 7-position.

5. The photoresist composition according to claim 1, wherein the photosensitive polymer comprises a first repeating unit represented by one of the structures of Formula 1-1: [Formula 1-1] Among them, In Formula 1-1, R 12 is hydrogen, C1 to C30 alkyl, C2 to C30 alkenyl, C2 to C30 alkynyl, C3 to C30 cycloalkyl, C1 to C30 alkoxy, C6 to C30 aryl, C3 to C30 heteroaryl, C7 to C30 aralkyl, or phenyl, X 12- is a non-metallic element or a compound anion, and * represents a binding site.

6. The photoresist composition according to claim 1, wherein the photosensitive polymer comprises a second repeating unit represented by one of the structures of Formula 2: [Formula 2] Among them, In formula 2, R 21 is a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C7-C30 aralkyl group, a substituted or unsubstituted C2-C30 acyl group, or a substituted or unsubstituted C7-C30 alkylbenzenesulfonyl group, R 22 is hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C2-C30 acyl group, a substituted or unsubstituted C7-C30 alkylbenzenesulfonyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C7-C30 aralkyl group, or a substituted or unsubstituted phenyl group, X 21- is a non-metallic element or a compound anion, and * represents a binding site.

7. The photoresist composition according to claim 6, wherein R 21 is a substituted C5 to C30 alkyl group as follows: at least one hydrogen atom bonded to the carbon atom at the 1, 5, or 6 position is replaced by a secondary or tertiary substituent, or the carbon atom at the 1, 5, or 6 position is replaced by a heteroatom-containing group.

8. The photoresist composition according to claim 6, wherein R 21 is a substituted or unsubstituted C5-C30 alkenyl group having a double bond between the carbon atom at the 4-position and the carbon atom at the 5-position, between the carbon atom at the 5-position and the carbon atom at the 6-position, or between the carbon atom at the 6-position and the carbon atom at the 7-position.

9. The photoresist composition according to claim 1, wherein the photosensitive polymer comprises a third repeating unit represented by one of the structures of Formula 3: [Formula 3] Among them, In formula 3, R 31 is a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C7-C30 aralkyl group, a substituted or unsubstituted C2-C30 acyl group, or a substituted or unsubstituted C7-C30 alkylbenzenesulfonyl group, R 32 and R 33 each independently is hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C2-C30 acyl group, a substituted or unsubstituted C7-C30 alkylbenzenesulfonyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C7-C30 aralkyl group, or a substituted or unsubstituted phenyl group, X 31- is a non-metallic element or compound anion, and * represents a binding site.

10. The photoresist composition according to claim 9, wherein R 31 is a substituted C5 to C30 alkyl group as follows: at least one hydrogen atom bonded to the carbon atom at the 1, 5, or 6 position is replaced by a secondary or tertiary substituent, or the carbon atom at the 1, 5, or 6 position is replaced by a heteroelement-containing group.

11. The photoresist composition according to claim 9, wherein R 31 is a substituted or unsubstituted C5 to C30 alkenyl group having a double bond between the carbon atom at the 4-position and the carbon atom at the 5-position, between the carbon atom at the 5-position and the carbon atom at the 6-position, or between the carbon atom at the 6-position and the carbon atom at the 7-position.

12. A photoresist composition, comprising: a photosensitive polymer; and a solvent, wherein the photosensitive polymer comprises a pyridinium salt and a functional group that can be converted into a free radical and is bonded to the pyridinium salt, and the functional group that can be converted into a free radical is included in the main chain of the photosensitive polymer.

13. The photoresist composition according to claim 12, wherein the photosensitive polymer comprises an eleventh repeating unit and a twelfth repeating unit, each of the eleventh repeating unit and the twelfth repeating unit being represented by one of the structures of Formula 1, and In Formula 1, the R of the eleventh repeating unit 11 is bonded to the binding site on the main chain of the twelfth repeating unit: [Formula 1] Among them, In Formula 1, The R of the twelfth repeating unit 11 is a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, or a substituted or unsubstituted C7-C30 aralkyl group, The R of the eleventh repeating unit 11 is a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C2-C30 alkenylene group, or a substituted or unsubstituted C7-C30 arylalkylene group. X 11- is a non-metallic element or a compound anion, and * represents the binding site.

14. The photoresist composition according to claim 12, wherein the photosensitive polymer comprises a twenty-first repeating unit and a twenty-second repeating unit, each of the twenty-first repeating unit and the twenty-second repeating unit being represented by one of the structures of Formula 2, and In Formula 2, the R of the twenty-first repeating unit 21 is bonded to the binding site on the main chain of the twenty-second repeating unit: [Formula 2] Among them, In Formula 2, The R of the twenty-second repeating unit 21 is a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C7-C30 aralkyl group, a substituted or unsubstituted C2-C30 acyl group, or a substituted or unsubstituted C7-C30 alkylbenzenesulfonyl group, The R of the twenty-first repeating unit 21 is a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C2-C30 alkenylene group, a substituted or unsubstituted C1-C30 alkyleneoxy group, a substituted or unsubstituted C7-C30 aralkyl group, a substituted or unsubstituted C2-C30 acyl group, or a substituted or unsubstituted C7-C30 divalent alkylbenzenesulfonyl group, R 22 is hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C2-C30 acyl group, a substituted or unsubstituted C7-C30 alkylbenzenesulfonyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C7-C30 aralkyl group, or a substituted or unsubstituted phenyl group, X 21- is a non-metallic element or a compound anion, and * represents the binding site.

15. The photoresist composition according to claim 12, wherein the photosensitive polymer comprises a thirty-first repeating unit and a thirty-second repeating unit, each of the thirty-first repeating unit and the thirty-second repeating unit being represented by one of the structures of Formula 3, and In Formula 3, the R of the thirty-first repeating unit 31 is bonded to the binding site on the main chain of the thirty-second repeating unit: [Formula 3] Among them, In Formula 3, The R of the 32nd repeating unit 31 is a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C7-C30 aralkyl group, a substituted or unsubstituted C2-C30 acyl group, or a substituted or unsubstituted C7-C30 alkylbenzenesulfonyl group, The R of the 31st repeating unit 31 is a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C2-C30 alkenylene group, a substituted or unsubstituted C1-C30 alkyleneoxy group, a substituted or unsubstituted C7-C30 aralkyl group, a substituted or unsubstituted C2-C30 acyl group, or a substituted or unsubstituted C7-C30 divalent alkylbenzenesulfonyl group. R 32 and R 33 each independently is hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C2-C30 acyl group, a substituted or unsubstituted C7-C30 alkylbenzenesulfonyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C7-C30 aralkyl group, or a substituted or unsubstituted phenyl group, X 31- is a non-metallic element or a compound anion, and * represents the binding site.

16. The photoresist composition according to any one of claims 1-15, further comprising a photoinitiator, the photoinitiator comprising a photo free radical generator.

17. The photoresist composition according to any one of claims 1-15, further comprising a radical quencher.

18. A method of manufacturing an integrated circuit device, the method comprising: forming a photoresist film on a feature layer by using the photoresist composition according to any one of claims 1-17; Free radicals are generated in the first region by exposing a first region that is part of the photoresist film to light, and a change in the polarity of the photosensitive polymer is caused by converting the pyridinium salt of the photosensitive polymer into a pyridine group; and A photoresist pattern including an unexposed region of the photoresist film is formed by removing the exposed first region from the photoresist film using a developer.

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