Photoresist composition and method for manufacturing integrated circuit element using the same

Abstract

To provide a photoresist composition that can provide excellent etching resistance and resolution in a photolithography process for manufacturing an integrated circuit element.SOLUTION: A photoresist composition according to the present invention has a photosensitive polymer and a solvent, where the photosensitive polymer includes a pyridinium salt and a functional group convertible into a radical bound to pyridinium salt, the functional group convertible into a radical includes an oxygen atom, a nitrogen atom or a carbon atom bound to a nitrogen atom of pyridinium salt, and generates a radical by 1,5-hydrogen atom transfer reaction, cyclization reaction in a molecule or decomposition reaction of multiple bonds.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a photoresist composition and a method for manufacturing an integrated circuit device using the same, and more particularly, to a photoresist composition containing a pyridinium salt and a method for manufacturing an integrated circuit device using the same.

Background Art

[0002] Due to the development of electronic technology, the down-scaling of integrated circuit devices has been rapidly advanced. Thereby, a photolithography process advantageous for realizing a fine pattern is required.

Summary of the Invention

Problems to be Solved by the Invention

[0003] The present invention has been made in view of the problems in the above-described conventional photolithography process, and an object of the present invention is to provide a photoresist composition capable of providing excellent etching resistance and resolution in a photolithography process for manufacturing an integrated circuit device. Another object of the present invention is to provide a method for manufacturing an integrated circuit device capable of improving the dimensional accuracy of a pattern to be formed by providing excellent etching resistance and resolution.

Means for Solving the Problems

[0004] The photoresist composition according to the present invention made to achieve the above object has a photosensitive polymer and a solvent, wherein the photosensitive polymer contains a pyridinium salt and a functional group convertible into a radical bonded to the pyridinium salt, and the functional group convertible into a radical contains an oxygen atom, a nitrogen atom or a carbon atom bonded to the nitrogen atom of the pyridinium salt, and is characterized in that radicals are generated by a decomposition reaction of the bond between the nitrogen atom of the pyridinium salt and the oxygen atom, nitrogen atom or carbon atom bonded to the nitrogen atom of the pyridinium salt.

[0005] Further, the photoresist composition according to an embodiment of the present invention has a photosensitive polymer and a solvent, wherein the photosensitive polymer contains a pyridinium salt and a functional group convertible into a radical bonded to the pyridinium salt, and the functional group convertible into a radical is contained in the main chain of the photosensitive polymer.

[0006] Also, a method for manufacturing an integrated circuit element according to an embodiment of the present invention includes a step of forming a photoresist film on a lower film using a photoresist composition containing a photosensitive polymer containing a pyridinium salt and a solvent, a step of exposing a first region which is a part of the photoresist film to generate radicals from the photosensitive polymer in the first region, and substituting the pyridinium salt of the photosensitive polymer with a pyridine group to induce a change in the polarity of the photosensitive polymer, and a step of removing the exposed first region from the photoresist film using a developer to form a photoresist pattern composed of a non-exposed region in the photoresist film.

Advantages of the Invention

[0007] According to the photoresist composition of the present invention, a chain decomposition reaction of the photosensitive polymer is induced by radicals generated by decomposition of the photosensitive polymer in the exposed area, causing a change in the polarity of the photosensitive polymer. At this time, due to the short lifetime and high reactivity of the radicals, the decomposition reaction of the photosensitive polymer in the non-exposed areas where the radicals penetrate into the non-exposed areas occurs relatively less, so the exposure sensitivity can be improved in the exposed areas of the photoresist film. This provides excellent resolution and improved sensitivity in the photolithography process, and by preventing the deterioration of the CD (critical dimension) distribution of the pattern obtained by the photolithography process, the dimensional accuracy of the pattern to be formed can be improved.

Brief Description of the Drawings

[0008]

Figure 1

Figure 2A

Figure 2B

Figure 2C

Figure 2D

Figure 2E

Modes for Carrying Out the Invention

[0009] Next, specific examples of modes for carrying out the photoresist composition according to the present invention will be described with reference to the drawings.

[0010] The same reference numerals are used for the same components in the drawings, and redundant descriptions thereof are omitted. In this specification, if a chemical bond is not drawn at a position where a chemical bond must be drawn in a chemical formula, it means that a hydrogen atom is bonded to the position unless otherwise defined.

[0011] A photoresist composition according to an embodiment of the present invention includes a photosensitive polymer and a solvent. In an embodiment, the photosensitive polymer includes a pyridinium salt and a functional group convertible to a radical bonded to the pyridinium salt. In this specification, the "functional group convertible to a radical" is a substituted or unsubstituted linear, cyclic, or mixed structure thereof having an oxygen atom, a nitrogen atom, or a carbon atom bonded to the nitrogen atom of the pyridinium salt. The term "substituted" as used herein means that at least one hydrogen bonded to carbon is substituted with a substituent or at least one carbon atom is substituted with a heteroatom-containing group, unless otherwise defined.

[0012] The substituent may include, for example, a halogen element, a hydroxy group, an aldehyde group, a carboxy group, an amino group, a cyano group, an isocyanate group, a thiol group, a sulfonic acid group, a phosphoric acid group, salts thereof, C1-C20 alkyl, C3-C20 cycloalkyl, C2-C20 alkenyl, C1-C20 alkoxy, C2-C20 alkenoxy, C6-C30 aryl, C6-C30 aryloxy, C7-C30 alkylaryl, or a C7-C30 alkylaryloxy group. 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-. However, the functional group convertible to a radical is not limited to the exemplified functional groups and may include various functional groups that generate radicals. In an exemplary embodiment, the functional group convertible to a radical generates a radical by a bond cleavage reaction between the nitrogen atom of the pyridinium salt and an oxygen atom, a nitrogen atom, or a carbon atom bonded to the nitrogen atom of the pyridinium salt through a 1,5-hydrogen atom transfer reaction or an intramolecular cyclization reaction.

[0013] In one embodiment, the photosensitive polymer includes a first repeating unit represented by any one of the structures of Chemical Formula 1 shown below. [Chemical Formula] In Chemical Formula 1, OR 11 is a functional group convertible to a radical. R 11 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, or a substituted or unsubstituted C7-C30 arylalkyl group. X 11 is a non-metallic element or an anionic compound. For example, X 11 may include OTs (4-methylbenzenesulfonate), BF4, or PF6. * is a bonding position.

[0014] In one embodiment, R 11 is a substituted C5-C30 alkyl group, but at least one hydrogen bonded to the carbon at the 1st, 5th, or 6th position is substituted with a secondary or higher substituent so that a 1,5-hydrogen atom transfer reaction occurs, or a functional group in which the carbon atom at the 1st, 5th, or 6th position is substituted with a hetero element-containing group. Substituents may include, for example, secondary amide, tertiary amide, secondary alcohol, tertiary alcohol, secondary alkyl halide, tertiary alkyl halide, secondary amine, tertiary amine, secondary ketimine, secondary aldimine, and the like. The heteroatom-containing group can be, 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-.

[0015] In one embodiment, R 11 is a substituted or unsubstituted C5-C30 alkenyl group, but is a functional group having a double bond between the 4th and 5th carbons, between the 5th and 6th carbons, or between the 6th and 7th carbons so that an intramolecular cyclization reaction occurs. For example, the photosensitive polymer contains a first repeating unit represented by the structure shown below. In the above structure, * is the bonding position.

[0016] In one embodiment, the photosensitive polymer contains a first repeating unit represented by any one of the structures of Chemical Formula 1-1 shown below.

Chemical Formula

[0017] In one embodiment, the photosensitive polymer contains a second repeating unit represented by any one of the structures of Chemical Formula 2 shown below.

Chemical formula

[0018] In one embodiment, R 21 is a substituted C5-C30 alkyl group, but at least one hydrogen bonded to the carbon at the 1st, 5th, or 6th position is substituted with a secondary or higher substituent or the carbon atom at the 1st, 5th, or 6th position is a functional group substituted with a heteroelement-containing group so that a 1,5-hydrogen atom transfer reaction occurs. The substituents 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, and the like. The heteroatom-containing group is, 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-. In one embodiment, R 21 is a substituted or unsubstituted C5-C30 alkenyl group, but may be a functional group having a double bond between the 4th and 5th carbons, between the 5th and 6th carbons, or between the 6th and 7th carbons so that an intramolecular cyclization reaction occurs.

[0019] For example, the photosensitive polymer includes a second repeating unit represented by the structure shown below. In the above structure, * is the bonding position.

[0020] In one embodiment, the photosensitive polymer includes a third repeating unit represented by any one of the structures of Chemical Formula 3 shown below.

Chemical formula

[0021] In one embodiment, R 31 is a substituted C5-C30 alkyl group, but at least one hydrogen bonded to the carbon at the 1st, 5th, or 6th position is substituted with a secondary or higher substituent or the carbon atom at the 1st, 5th, or 6th position is a functional group substituted with a hetero element-containing group so that a 1,5-hydrogen atom transfer reaction occurs. Substituents include, for example, secondary amide, tertiary amide, secondary alcohol, tertiary alcohol, secondary alkyl halide, tertiary alkyl halide, secondary amine, tertiary amine, secondary ketimine, secondary aldimine, and the like. Hetero element-containing groups are, 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-. In one embodiment, R 31 is a substituted or unsubstituted C5-C30 alkenyl group, but is a functional group having a double bond between the 4th and 5th carbons, between the 5th and 6th carbons, or between the 6th and 7th carbons so that an intramolecular cyclization reaction occurs.

[0022] In an exemplary embodiment, the photosensitive polymer includes a main chain scission (MCS) structure that forms free radicals in the main chain to induce main chain scission. In an exemplary embodiment, the photosensitive polymer includes a functional group convertible to a radical in the main chain. In an exemplary embodiment, the photosensitive polymer includes an 11th repeating unit and a 12th repeating unit represented by any one of the structures of Chemical Formula 1 described above. The 11th repeating unit and the 12th repeating unit are each independently R selected from a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, or a substituted or unsubstituted C7-C30 arylalkyl group. 11 including. In one embodiment, R of the 11th repeating unit in the photosensitive polymer 11 is bonded to the bonding position of the main chain of the 12th repeating unit. For example, the photosensitive polymer is -[C2H3] n -R 11 -O-bond. For example, -[C2H3] n -R 11 -O-in, "n" is a natural number within 1 to 100.

[0023] In another exemplary embodiment, the photosensitive polymer includes an 11th repeating unit and a 12th repeating unit represented by any one of the structures of Chemical Formula 1-1 described above. The 11th repeating unit and the 12th repeating unit are each independently selected from 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 C6-C30 aryl group, a substituted or unsubstituted C6-C30 heteroaryl group, a substituted or unsubstituted C7-C30 arylalkyl group, or a substituted or unsubstituted phenyl group.12 including In one embodiment, R of the 11th repeating unit is bonded to the bonding position of the main chain of the 12th repeating unit within the photosensitive polymer 12 in the photosensitive polymer. For example, the photosensitive polymer contains -[C2H3] n -R 12 -O- bond. For example, -[C2H3] n -R 12 -O-, where "n" is a natural number within 1 to 100.

[0024] In one embodiment, the photosensitive polymer contains a 4th repeating unit represented by Chemical Formula 4 shown below.

Chemical Formula

[0025] In an exemplary embodiment, R 41 and R 42 contain functional groups as exemplified by R 11 in Chemical Formula 1 described above. R 41 and R 42is a substituted C5-C30 alkyl group, but at least one hydrogen bonded to the carbon at the 1st, 5th, or 6th position is substituted with a secondary or higher substituent, or the carbon atom at the 1st, 5th, or 6th position is a functional group substituted with a heteroelement-containing group, or a substituted or unsubstituted C5-C30 alkenyl group, and may also be a functional group having a double bond between the 4th and 5th carbons, between the 5th and 6th carbons, or between the 6th and 7th carbons. For example, the photosensitive polymer contains a fourth repeating unit represented by the structure shown below. TIFF2025110889000009.tif68128In the above structure, * is the bonding position.

[0026] In another exemplary embodiment, the photosensitive polymer contains a 21st repeating unit and a 22nd repeating unit represented by any one of the structures of Chemical Formula 2 described above. The 21st repeating unit and the 22nd repeating unit are each independently a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, or a substituted or unsubstituted C7-C30 arylalkyl group, a substituted or unsubstituted C2-C30 acetyl group, or a substituted or unsubstituted C7-C30 tosyl group, and R 21 is included. In one embodiment, R of the 21st repeating unit in the photosensitive polymer 22 is bonded to the bonding position of the main chain of the 22nd repeating unit. For example, the photosensitive polymer contains -[C2H3] n -R 22 -N-bond.

[0027] In one embodiment, the photosensitive polymer contains a fifth repeating unit represented by Chemical Formula 5 shown below.

Chemical Formula

[0028] In an exemplary embodiment, R 51 and R 53 contain a functional group as exemplified by R 21 in Chemical Formula 2 described above. R 51 and R 53 is a substituted C5-C30 alkyl group, wherein at least one hydrogen bonded to the carbon at the 1st, 5th, or 6th position is substituted with a secondary or higher substituent, a functional group in which the carbon atom at the 1st, 5th, or 6th position is substituted with a heteroelement-containing group, or a substituted or unsubstituted C5-C30 alkenyl group having a double bond between the 4th and 5th carbons, between the 5th and 6th carbons, or between the 6th and 7th carbons.

[0029] In other exemplary embodiments, the photosensitive polymer includes a 31st repeating unit and a 32nd repeating unit represented by any one of the structures of Chemical Formula 3 described above. The 31st repeating unit and the 32nd repeating unit are each independently a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, or a substituted or unsubstituted C7-C30 arylalkyl group, a substituted or unsubstituted C2-C30 acetyl group, or a substituted or unsubstituted C7-C30 tosyl group, R 31 containing. In one embodiment, R of the 31st repeating unit in the photosensitive polymer 32 is bonded to the bonding position of the main chain of the 32nd repeating unit. For example, the photosensitive polymer is -[C2H3] n -R 32 -C-bond.

[0030] In one embodiment, the photosensitive polymer includes a 6th repeating unit represented by Chemical Formula 6 shown below.

Chemical formula

[0031] In an exemplary embodiment, R 61 and R 64 contain functional groups as exemplified by R 31 in Chemical Formula 3 described above. R 61 and R 64 are substituted C5-C30 alkyl groups, where at least one hydrogen bonded to the carbon at the 1st, 5th, or 6th position is substituted with a secondary or higher substituent, or the carbon atom at the 1st, 5th, or 6th position is substituted with a heteroelement-containing group, or functional groups that are substituted or unsubstituted C5-C30 alkenyl groups having a double bond between the 4th and 5th carbons, between the 5th and 6th carbons, or between the 6th and 7th carbons.

[0032] In an exemplary embodiment, the photosensitive polymer contains at least one repeating unit selected from the first repeating unit, the second repeating unit, the third repeating unit, the fourth repeating unit, the fifth repeating unit, and the sixth repeating unit. For example, the photosensitive polymer may contain a combination of the first repeating unit and the second repeating unit, a combination of the first repeating unit and the third repeating unit, and the like.

[0033] The solvent contained in the photoresist composition consists of an organic solvent. The organic solvent may include, but is not limited to, at least one of ether, alcohol, glycol ether, aromatic hydrocarbon compound, ketone, and ester. For example, the organic solvent may consist of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl ether, diethylene glycol ethyl 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, ethyl alcohol, propanol, isopropyl alcohol, isobutyl alcohol, 4-methyl-2-pentanol (methyl isobutyl carbion: MIBC), hexanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol, propylene glycol, heptanone, propylene carbonate, butylene carbonate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 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, gamma-butyrolactone, methyl 2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionic acid, ethoxyethoxypropionic acid, or a combination thereof.

[0034] In the photoresist composition according to an embodiment of the present invention, the solvent may be included as the remaining amount excluding the content of the main components including a photosensitive polymer and the like. In an exemplary embodiment, the solvent is included in an amount of about 70% by weight to about 99.8% by weight based on the total weight of the photoresist composition, but is not limited thereto. In one embodiment, the photoresist composition may further include a photoinitiator. The photoinitiator is configured to absorb light and generate radicals. For example, the photoinitiator consists of a PRG (photoradical generator) configured to generate radicals upon exposure. The photoinitiator absorbs light in the exposed area of the photoresist film after the photoresist film obtained from the photoresist composition is exposed to light, and generates radicals. The radicals generated from the photoinitiator may react with the first to sixth repeating units of the photosensitive polymer. Therefore, when the photoresist composition according to an embodiment of the present invention contains a photoinitiator, a radical chain reaction of the photosensitive polymer described below occurs due to the radicals generated from the photoinitiator.

[0035] When the photoresist composition according to an embodiment of the present invention contains a photoinitiator, the photoinitiator can compensate for the relatively low reactivity of the photoresist composition when the photoresist film obtained from the photoresist composition is exposed, and the sensitivity to light in the exposed area of the photoresist film is adjusted according to the content of the photoinitiator. In particular, the photoinitiator can be induced to cause a photoreaction only in the exposed area of the photoresist film by promoting a radical chain reaction in the photoresist composition using radicals in the exposed area of the photoresist film. When the above PRG is exposed to any one of light selected from a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F2 excimer laser (157 nm), and an EUV laser (13.5 nm), it can absorb the light and generate radicals, thereby initiating the polymerization of the organometallic compound contained in the photoresist composition according to the embodiments of the present invention.

[0036] In an exemplary embodiment, the PRG can consist of an acylphosphine oxide-based compound, an oxime ester-based compound, and the like. Examples of acylphosphine oxide-based compounds include 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.

[0037] Examples of the oxime ester compounds include 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-dioxolane-4-yl)methyloxy]benzoyl]-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, and the like.

[0038] In other exemplary embodiments, commercially available products (products of BASF, trade names), such as IRGACURE® 651, IRGACURE® 184, IRGACURE® 1173, IRGACURE® 2959, IRGACURE® 127, IRGACURE® 907, IRGACURE® 369, IRGACURE® 379, IRGACURE® TPO, IRGACURE® 819, IRGACURE® OXE01, IRGACURE® OXE02, IRGACURE® MBF, or IRGACURE® 754, etc., can be used as the PRG.

[0039] The photoresist composition according to the technical idea of the present invention may not contain a photoinitiator, may contain a single substance selected from among the PRGs as a photoinitiator, or may contain at least two substances selected from among the PRGs. When a photoinitiator is included in the photoresist composition according to an embodiment of the present invention, the photoinitiator may be included in an amount of about 0.02% by weight to about 10% by weight based on the total amount of the photoresist composition, but is not limited thereto.

[0040] In an exemplary embodiment, when the PRG is included as a photoinitiator in the photoresist composition according to an embodiment of the present invention, the photoresist composition may further include a radical quencher that can trap radicals. In an exemplary embodiment, the radical quencher consists of a quinone type free radical or a nitroxide (IUPAC name: aminoxyl) free radical. Quinone-type free radicals can include, but are not limited to, p-benzoquinone, hydroquinone (1,4-dihydroxybenzene), hydroquinone monomethyl ether (4-methoxyphenol), hydroquinone monomethyl ether, hydroquinone monophenyl ether, MTBHQ (mono-t-butyl hydroquinone), di-t-butyl hydroquinone, di-t-amyl hydroquinone, toluhydroquinone, 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-anilino-quinoline-5,8-quinone, pyrroloquinoline quinone, 2-allyl-6-methoxybenzo-1,4-quinone, or combinations thereof.

[0041] Nitroxide free radicals can include, but are not limited to, DTBN (di-tert-butyl nitroxide), TEMPO (2,2,6,6-tetramethyl-1-peperidine 1-oxyl), oxo-TEMPO (4-oxo-2, 2, 6, 6-tetramethyl-1-peperidine 1-oxyl), 1,1,3,3-tetraethylisoindolin-N-oxyl, SG1 (N-tert-butyl-N-[1-(diethoxyphosphoryl)-2,2-dimethylpropyl]aminoxyl), TIPNO (N-tert-butyl-N-(2-methyl-1-phenylpropyl)aminoxyl), or combinations thereof.

[0042] In an exemplary embodiment, the photoresist composition according to an embodiment of the present invention may further include at least one selected from a leveling agent, a surfactant, a dispersant, a moisture absorbent, and a coupling agent. The leveling agent is used to improve the coating flatness when coating the photoresist composition on a substrate, and a known leveling agent available by a commercial method can be used.

[0043] The surfactant plays a role in improving the coating uniformity of the photoresist composition and improving the wettability. In an exemplary embodiment, the surfactant can consist of, but is not limited to, sulfate salts, sulfonate salts, phosphate esters, soaps, amine salts, quaternary ammonium salts, polyethylene glycols, alkylphenol ethylene oxide adducts, polyhydric alcohols, nitrogen-containing vinyl polymers, or combinations thereof. For example, the surfactant can include alkylbenzene sulfonate salts, alkylpyridinium salts, polyethylene glycols, or quaternary ammonium salts. When the photoresist composition contains a surfactant, the surfactant can be contained in an amount of about 0.001 wt% to about 3 wt% based on the total weight of the photoresist composition.

[0044] The dispersant serves to uniformly disperse each component constituting the photoresist composition within the photoresist composition. In an exemplary embodiment, the dispersant can consist of, but is not limited to, epoxy resins, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, glucose, sodium dodecyl sulfate, sodium citrate, oleic acid, linoleic acid, or combinations thereof. When the photoresist composition contains a dispersant, the dispersant can be contained in an amount of about 0.001 wt% to about 5 wt% based on the total weight of the photoresist composition.

[0045] The moisture absorbent serves to prevent the adverse effects caused by moisture in the photoresist composition. In an exemplary embodiment, the moisture absorbent may consist of, but is not limited to, polyoxyethylene nonylphenol ether, polyethylene glycol, polypropylene glycol, polyacrylamide, or a combination thereof. When the photoresist composition contains a moisture absorbent, the moisture absorbent may be included in an amount of about 0.001 wt% to about 10 wt% based on the total weight of the photoresist composition.

[0046] The coupling agent plays a role in improving the adhesion to the underlying film when the photoresist composition is coated on the underlying film. In an exemplary embodiment, the coupling agent includes a silane coupling agent. The silane coupling agent may consist of, 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 contains a coupling agent, the coupling agent may be included in an amount of about 0.001 wt% to about 5 wt% based on the total weight of the photoresist composition.

[0047] When the photoresist film obtained from the photoresist composition containing the photosensitive polymer according to an embodiment of the present invention is exposed, the photoresist composition absorbs light, and a functional group convertible to a radical from the pyridinium salt of the photosensitive polymer is eliminated. As a result, the pyridinium salt of the photosensitive polymer is substituted with a pyridine group, and a change in the polarity of the photosensitive polymer is induced.

[0048] The process of generating radicals from functional groups convertible to radicals is explained as follows. Exposure of the photoresist film generates secondary electrons, and the N-O bond of -N-OR in the first repeating unit of the photosensitive polymer contained in the exposed photoresist film by the secondary electrons 11 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 )(R 32 )(R 33 ) in the third repeating unit is decomposed. Alternatively, radicals are generated by a photoinitiator contained in the photoresist composition, and the N-O bond of -N-OR in the first repeating unit of the photosensitive polymer contained in the exposed photoresist film by the radicals 11 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 )(R 32 )(R 33 ) in the third repeating unit is decomposed.

[0049] The decomposition of the N-O bond of -N-OR in the first repeating unit, the N-N bond of -N-N(R 11 )(R 21 ) in the second repeating unit or the N-C bond of -N-C(R 22 )(R 31 )(R 32 )(R 33 ) in the third repeating unit generates radicals having unshared hole electrons. For example, the N-O bond of -N-OR in the first repeating unit is decomposed to generate a radical consisting of HO-R 11 again, the N-N bond of -N-N(R 11 )(R 21 ) in the second repeating unit is decomposed to generate a radical consisting of HN-R 22 (R 21 )(R 22 )·, and the N-C bond of -N-C(R 31 )(R 32 )(R33 ) The N-C bond is decomposed, and HC-R 31 (R 32 )(R 33 )· A radical consisting of is generated. In this specification, "·" means an unshared hole electron. At this time, R 11 , R 21 , or R 31 contains a functional group capable of a 1,5-hydrogen atom transfer reaction or an intramolecular cyclization reaction, a radical is generated through a 1,5-hydrogen atom transfer reaction or an intramolecular cyclization reaction.

[0050] Thereafter, in the first repeating unit in which a functional group convertible to a radical has been eliminated, the second repeating unit, or the first repeating unit, the second repeating unit, or the third repeating unit to which a functional group convertible to a radical around the third repeating unit is bonded, a radical binds to the ortho position of the pyridinium salt contained therein, and due to the binding of the radical, a functional group convertible to a radical is eliminated from the pyridinium salt to generate a new radical, so a chain decomposition reaction of the photosensitive polymer can occur. Specifically, HO-R 11 · binds to the ortho position of the pyridinium salt of the first repeating unit, and the N-O bond of -N-OR 11 is decomposed, and a radical consisting of HO-R 11 · is generated again, and HN-R 21 (R 22 )· binds to the ortho position of the pyridinium salt of the second repeating unit, and the N-N bond of -N-N(R 21 )(R 22 ) is decomposed, and a radical consisting of HN-R 21 (R 22 )· is generated again, and HC-R 31 (R 32 )(R 33 )· binds to the ortho position of the pyridinium salt of the third repeating unit, and the N-C bond of -N-C(R 31 )(R 32 )(R 33 ) is decomposed, and HC-R 31 (R 32 )(R 33)· generates a radical. That is, the N - O bond of -N-OR in the first repeating unit, 11 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 )(R 32 )(R 33 ) in the third repeating unit undergoes a chain decomposition reaction.

[0051] For example, when a photoresist film obtained from a photoresist composition containing the photosensitive polymer represented by Chemical Formula 1 described above is exposed, the chain decomposition reaction of the N - O bond of -N-OR in the first repeating unit is represented by Reaction Formula 1 shown below. 11 The chain decomposition reaction of the N - O bond of -N-OR in the first repeating unit of the photosensitive polymer by radicals is represented by Reaction Formula 1 shown below. [Chemical Formula]

[0052] By the chain decomposition reaction of the photosensitive polymer by radicals, the first repeating unit in the photosensitive polymer is converted to a structure in which -R 11 OH is bonded to the ortho position of the pyridine group, a structure in which a substance selected from the PRGs added by a photoinitiator is bonded to the ortho position of the pyridine group, or a structure containing a pyridine group in a structure containing a pyridinium salt. Also, the second repeating unit is converted to a structure in which -R 21 -N(R 22 )(H) is bonded to the ortho position of the pyridine group, a structure in which a substance selected from the PRGs added by a photoinitiator is bonded to the ortho position of the pyridine group, or a structure containing a pyridine group in a structure containing a pyridinium salt. Also, the third repeating unit is converted to a structure in which -R 31 C(R 32 )(R 33) is converted into a structure to which a substance selected from a structure in which a PRG added by a photoinitiator is bonded to the ortho position of a pyridine group, or a structure containing a pyridine group.

[0053] For example, when a photoresist film obtained from a photoresist composition containing the photosensitive polymer represented by the above-described Chemical Formula 1 is exposed, a reaction as shown in Reaction Formula 2 below occurs, and the first repeating unit of the above-described Chemical Formula 1 is converted to include a structure as represented by the product of Reaction Formula 2 shown below.

Chemical Formula

[0054] For example, when a photoresist film obtained from a photoresist composition containing the photosensitive polymer represented by the above-described Chemical Formula 2 is exposed, a reaction as shown in Reaction Formula 3 below occurs, and the second repeating unit of the above-described Chemical Formula 2 is converted to include a structure as represented by the product of Reaction Formula 3 shown below.

Chemical Formula

[0055] A photoresist composition according to an exemplary embodiment according to the technical idea of the present invention includes a photosensitive polymer containing a functional group convertible to a radical. In the exposure step, a decomposition reaction of the photosensitive polymer and a chain decomposition reaction of the photosensitive polymer are induced using radicals generated by the decomposition reaction of the photosensitive polymer. The photosensitive polymer contains a pyridinium salt, but since the pyridinium salt of the photosensitive polymer is substituted with a pyridine group by elimination of a functional group convertible to a radical, the photosensitive polymer is converted to a property soluble in a developer. At this time, due to the high reactivity and short lifetime of the radicals, the decomposition reaction of the photosensitive polymer in the non-exposed area, which may occur due to the penetration of the radicals into the non-exposed area, occurs relatively less, so the exposure sensitivity is improved in the exposed area of the photoresist film. This provides excellent resolution and improved sensitivity in the photolithography process, and improves the dimensional accuracy of the pattern to be formed by preventing the deterioration of the CD (critical dimension) distribution of the pattern obtained by the photolithography process.

[0056] Alternatively, when the photosensitive polymer contains at least any one of the fourth to sixth repeating units during the exposure of the photoresist film, -N-OR contained in the fourth repeating unit 41 The N-O bond of -, -N-N(R 51 )(R 52 )- contained in the fifth repeating unit, or the N-N bond, or -N-C(R 61 )(R 62 )(R 63 )- in the sixth repeating unit is decomposed. The process in which the functional group convertible to a radical is eliminated from the pyridinium salt of the photosensitive polymer, a radical is generated from the functional group convertible to a radical, and the main chain of the photosensitive polymer is decomposed is explained as follows. Secondary electrons are generated by the exposure of the photoresist film, and the N-O bond of -N-OR in the fourth repeating unit of the photosensitive polymer contained in the photoresist film exposed by the secondary electrons 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 is decomposed. Alternatively, radicals are generated by a photoinitiator contained in the photoresist composition, and the N-O bond of -N-OR in the fourth repeating unit of the photosensitive polymer contained in the photoresist film exposed by the radicals 41 The N-N bond of -, -N-N(R 51 )(R 52) - N-N bond, or -N-C(R at the 6th repeating unit 61 )(R 62 )(R 63 ) - N-C bond is decomposed.

[0057] For example, when a photoresist film obtained from a photoresist composition containing the photosensitive polymer represented by the above-described Chemical Formula 4 is exposed, a reaction as shown in Reaction Formula 4 below occurs, and the 4th repeating unit of the above-described Chemical Formula 4 is converted to include a structure as represented by the product of Reaction Formula 4 shown below.

Chemical Formula

[0058] When the photoresist composition according to an exemplary embodiment according to the technical idea of the present invention contains a photosensitive polymer having an MCS (main chain scission) structure, the main chain of the photosensitive polymer is cleaved by the exposure process, so the molecular weight of the photosensitive polymer decreases, and the exposure sensitivity improves in the exposed area of the photoresist film. Thereby, excellent resolution and improved sensitivity are provided in the photolithography process, and by preventing deterioration of the CD distribution of the pattern obtained by the photolithography process, the dimensional accuracy of the pattern to be formed is improved.

[0059] The photosensitive polymer contained in the photoresist composition according to an exemplary embodiment according to the technical idea of the present invention is synthesized through the following synthesis method. However, the synthesis method of the photosensitive polymer described below is merely an example, and the photosensitive polymer can be synthesized through various synthesis methods.

[0060] In one embodiment, the photosensitive polymer containing the first repeating unit is synthesized through a reaction as shown in Synthesis Formula 1 below.

Chemical Formula

[0061] In one embodiment, a photosensitive polymer containing a second repeating unit is synthesized through a reaction as shown in Synthesis Formula 2 below.

Chemical Formula

[0062] In one embodiment, poly(4-ethenylpyridine) is synthesized through the polymerization reaction of 4-ethenylpyridine. Subsequently, NH2-A (A is a non-metallic element or an anionic compound), TsCl, a base, and R 21 OTs (4-methylbenzenesulfonate) are added in sequence to synthesize a photosensitive polymer containing a second repeating unit. In other embodiments, using NH2-C5H4N-CH=CH2 as a monomer, TsCl, a base, and R 21 OTs (4-methylbenzenesulfonate) are added in sequence to synthesize a photosensitive polymer containing a second repeating unit, or using Ts-N-C5H4N-CH=CH2 as a monomer, R 21 OTs (4-methylbenzenesulfonate) is added to synthesize a photosensitive polymer containing a second repeating unit.

[0063] In one embodiment, a photosensitive polymer containing a third repeating unit is synthesized through a reaction as shown in Synthesis Formula 3 below.

Chem.

[0064] In one embodiment, poly(4-vinylpyridine) is synthesized through the polymerization reaction of 4-ethenylpyridine, and then, through the alkylation reaction and the anion exchange reaction in sequence, a photosensitive polymer containing a third repeating unit is synthesized. Or, in another embodiment, R 31 -CH2-C5H4N-CH=CH2 is used as a monomer to synthesize a photosensitive polymer containing a third repeating unit through an anion exchange reaction.

[0065] In one embodiment, a photosensitive polymer containing a fourth repeating unit is synthesized through a reaction as shown in Synthesis Formula 4 below.

Chem.

[0066] Hereinafter, a method for manufacturing an integrated circuit element using a photoresist composition according to an embodiment of the present invention will be described with specific examples. FIG. 1 is a flowchart for explaining a method for manufacturing an integrated circuit element according to an embodiment of the present invention, and FIGS. 2A to 2E are cross-sectional views showing the steps in sequence for explaining a method for manufacturing an integrated circuit element according to an embodiment of the present invention.

[0067] Referring to FIGS. 1 and 2A, in step P10, a feature layer 110 is formed on a substrate 100. Thereafter, in step P20, a photoresist film 130 is formed on the feature layer 110 using the photoresist composition according to an embodiment of the present invention. The more detailed configuration of the photoresist composition is as described above. The substrate 100 includes a semiconductor substrate. The feature layer 110 is an insulating film, a conductive film, or a semiconductor film. For example, the feature layer 110 may be made of metal, alloy, metal carbide, metal nitride, metal oxynitride, metal oxycarbide, semiconductor, polysilicon, oxide, nitride, oxynitride, or a combination thereof, but is not limited thereto.

[0068] In an exemplary embodiment, as illustrated in FIG. 2A, before forming the photoresist film 130 on the feature layer 110, a lower film 120 is formed on the feature layer 110. In that case, the photoresist film 130 is formed on the lower film 120. The lower film 120 prevents the photoresist film 130 from being adversely affected by the underlying feature layer 110. In an exemplary embodiment, the lower film 120 may be made of an organic or inorganic ARC (anti-reflective coating) material for KrF excimer laser, ArF excimer laser, EUV laser, or any other light source.

[0069] In an exemplary embodiment, the lower film 120 may be a BARC (bottom anti-reflective coating) film or a DBARC (developable bottom anti-reflective coating) film. In another exemplary embodiment, the lower film 120 may include an organic component having an absorptive structure. The absorptive structure is, for example, a hydrocarbon compound having one or more benzene rings or a structure in which benzene rings are condensed. The lower film 120 is formed to have a thickness of about 1 nm to about 100 nm, but is not limited thereto. In an exemplary embodiment, the lower film 120 can be omitted.

[0070] To form the photoresist film 130, after coating the lower film 120 with the photoresist composition according to an embodiment of the present invention, heat treatment is performed. The above coating can be performed by methods such as spin coating, spray coating, dip coating, etc. The step of heat-treating the photoresist composition is performed at a temperature of about 80°C to about 300°C for about 10 seconds to about 100 seconds, but is not limited thereto. The thickness of the photoresist film 130 is several tens to several hundreds of times the thickness of the lower film 120. The photoresist film 130 is formed to have a thickness of about 10 nm to about 1 μm, but is not limited thereto.

[0071] Referring to FIGS. 1 and 2B, in step P30, a first region 132, which is a part of the photoresist film 130, is exposed. As a result, in the first region 132, the radical generation reaction and the decomposition reaction of the photosensitive polymer contained in the photoresist film 130 as described above are induced. Specifically, in step P30 of FIG. 1, when a first region 132, which is a part of the photoresist film 130, is exposed, radicals are generated from a functional group that can be converted into a radical bonded to the pyridinium salt of the photosensitive polymer in the first region 132, a functional group containing a functional group that can be converted into a radical from the pyridinium salt of the photosensitive polymer is eliminated, the pyridinium salt of the photosensitive polymer is substituted with a pyridine group, and a change in the polarity of the photosensitive polymer is induced. Since a second region 134, which is a part of the photoresist film 130, is not exposed, the photosensitive polymer is retained as a structure containing a pyridinium salt. Thereby, the solubility difference in the developer between the first region 132 and the second region 134 of the photoresist film 130 becomes large.

[0072] Due to the high reactivity and short lifetime of the radicals generated by the elimination of the functional groups convertible to radicals in the photosensitive polymer, the decomposition reaction of the photosensitive polymer in the non-exposed areas caused by the penetration of the radicals into the non-exposed areas occurs relatively less, so the exposure sensitivity is improved in the exposed areas of the photoresist film. Thereby, excellent resolution and improved sensitivity are provided in the photolithography process, and by preventing the deterioration of the CD (critical dimension) distribution of the pattern obtained by the photolithography process, the dimensional accuracy of the pattern to be formed is improved.

[0073] In another exemplary embodiment, when the photoresist film 130 contains a photoinitiator, if the first region 132, which is a part of the photoresist film 130, is exposed by the process P30 in FIG. 1, radicals are generated from the photoinitiator in the first region 132. The photoinitiator can consist of a PRG configured to generate radicals upon exposure to light. Therefore, while the first region 132 of the photoresist film 130 is being exposed by the process P30 in FIG. 1, the photoinitiator contained in the photoresist film 130 absorbs light and generates radicals from the first region 132.

[0074] In an exemplary embodiment, in order to expose the first region 132 of the photoresist film 130, a photomask 140 having a plurality of light shielding areas LS and a plurality of light transmitting areas LT is aligned at a predetermined position on the photoresist film 130, and the first region 132 of the photoresist film 130 is exposed through the plurality of light transmitting areas LT of the photomask 140. To expose the first region 132 of the photoresist film 130, 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) can be used.

[0075] In an exemplary embodiment, the photomask 140 includes a transparent substrate 142 and a plurality of light-shielding patterns 144 formed in a plurality of light-shielding regions LS on the transparent substrate 142. The transparent substrate 142 may be made of quartz. The plurality of light-shielding patterns 144 may be made of chromium (Cr). A plurality of light-transmitting regions LT are defined by the plurality of light-shielding patterns 144. According to the technical idea of the present invention, in order to expose the first region 132 of the photoresist film 130, a reflective photomask (not shown) for EUV exposure may be used instead of the photomask 140. Thereafter, heat is applied to the photoresist film 130 including the exposed first region 132 to perform a bake process. The bake process is performed at a temperature of about 50°C to about 400°C for about 10 seconds to about 150 seconds. For example, the bake process is performed at a temperature of about 150°C to about 250°C for about 60 seconds to about 120 seconds, but is not limited thereto. The bake process may be omitted depending on the process.

[0076] Referring to FIGS. 1 and 2C, in step P40, the photoresist film 130 is developed using a developer to remove the first region 132 of the photoresist film 130. As a result, a photoresist pattern 130P composed of the unexposed second region 134 of the photoresist film 130 is formed. The photoresist pattern 130P includes a plurality of openings OP. After the photoresist pattern 130P is formed, the portions of the lower film 120 exposed through the plurality of openings OP are removed to form a lower pattern 120P. In an exemplary embodiment, the development of the photoresist film 130 is performed by an NTD (negative-tone development) process.

[0077] In an exemplary embodiment, a developer composed of an organic solvent is used to develop the photoresist film 130. For example, as the developer, it has ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, methanol, esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, aromatic compounds such as benzene, xylene, toluene, or combinations thereof, but is not limited thereto. In an exemplary embodiment, an alkaline developer is used to develop the photoresist film 130. The alkaline developer may consist of a 2.38 wt% tetramethylammonium hydroxide (TMAH) solution.

[0078] As described with reference to FIG. 2B, as the solubility difference between the first region 132 exposed in the photoresist film 130 and the unexposed second region 134 with respect to the developer increases, while developing the photoresist film 130 to remove the first region 132, the second region 134 is not removed and remains as it is. Therefore, after developing the photoresist film 130, no residual defects such as a footing phenomenon occur, and a vertical sidewall profile is obtained from the photoresist pattern 130P. By improving the sidewall profile of the photoresist pattern 130P in this way, when processing the feature layer 110 using the photoresist pattern 130P, the critical dimension of the intended processing region in the feature layer 110 can be precisely controlled.

[0079] In an exemplary embodiment, after developing the photoresist film 130 to form the photoresist pattern 130P, a step of further performing a hard bake treatment on the obtained result is executed. Through the hard bake process, unnecessary substances such as the developer remaining on the result on which the photoresist pattern 130P is formed are removed. The hard bake process is carried out at a temperature of about 50°C to about 400°C for about 10 seconds to about 150 seconds. For example, the hard bake process is carried out at a temperature of about 150°C to about 250°C for about 60 seconds to about 120 seconds, but is not limited thereto.

[0080] Referring to FIGS. 1 and 2D, in step P50, the feature layer 110 is processed using the photoresist pattern 130P in the result of FIG. 2C. To process the feature layer 110, various processes are performed, such as etching the feature layer 110 exposed through the opening OP of the photoresist pattern 130P, implanting impurity ions into the feature layer 110, forming an additional film on the feature layer 110 through the opening OP, and deforming a part of the feature layer 110 through the opening OP. FIG. 2D illustrates a case where the feature layer 110 exposed through the opening OP is etched to form the feature pattern 110P as an exemplary process for processing the feature layer 110, but the technical idea of the present invention is not limited thereto.

[0081] In another exemplary embodiment, in the process described with reference to FIG. 2A, the formation process of the feature layer 110 is omitted. In that case, instead of the process of step P50 in FIG. 1 and the process described with reference to FIG. 2D, the substrate 100 is processed using the photoresist pattern 130P. For example, various processes are performed using the photoresist pattern 130P, such as etching a part of the substrate 100, implanting impurity ions into a part of the substrate 100, forming an additional film on the substrate 100 through the opening OP, and deforming a part of the substrate 100 through the opening OP.

[0082] Referring to FIG. 2E, the photoresist pattern 130P and the lower pattern 120P remaining on the feature pattern 110P in the result of FIG. 2D are removed. To remove the photoresist pattern 130P and the lower pattern 120P, ashing and strip processes can be used.

[0083] According to the method for manufacturing an integrated circuit device according to the technical idea of the present invention described with reference to FIGS. 1 and 2A to 2E, the solubility difference in the developer between the exposed region and the unexposed region of the photoresist film 130 obtained using the photoresist composition according to the technical idea of the present invention becomes large, and the CD distribution in the photoresist pattern 130P is improved. Therefore, when performing subsequent processes on the feature layer 110 and / or the substrate 100 using the photoresist pattern 130P, the critical dimensions of the processing region or pattern to be formed on the feature layer 110 and / or the substrate 100 are precisely controlled to improve dimensional accuracy. In addition, the CD distribution of the pattern to be embodied on the substrate 100 is uniformly controlled, and the productivity of the manufacturing process of the integrated circuit device is improved.

[0084] Note that the present invention is not limited to the above-described embodiments. Various modifications can be made without departing from the technical scope of the present invention.

Explanation of Reference Numerals

[0085] 100 Substrate 110 Feature layer 110P Feature pattern 120 Lower film 120P Lower pattern 130 Photoresist film 130P Photoresist pattern 132 First region 134 Second region 140 Photomask 142 Transparent substrate 144 Light-shielding pattern

Claims

1. A photosensitive polymer and, a solvent, and has, The photosensitive polymer includes a pyridinium salt and a functional group convertible to a radical bonded to the pyridinium salt. The functional group convertible to a radical includes an oxygen atom, a nitrogen atom, or a carbon atom bonded to the nitrogen atom of the pyridinium salt. A photoresist composition, characterized in that radicals are generated by a decomposition reaction of a bond between the nitrogen atom of the pyridinium salt and an oxygen atom, a nitrogen atom, or a carbon atom bonded to the nitrogen atom of the pyridinium salt.

2. The photoresist composition according to claim 1, wherein the photosensitive polymer includes a first repeating unit represented by any one of the structures of Chemical Formula 1 below. 【Chemical 1】 In the above chemical formula 1, R １１ 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, or a substituted or unsubstituted C7-C30 arylalkyl group, and X １１ is a non-metallic element or an anionic compound, and * is the bonding position.

3. Said R １１ is a substituted C5-C30 alkyl group, wherein at least one hydrogen bonded to the carbon at the 1st, 5th, or 6th position is substituted with a secondary or higher substituent, or the carbon atom at the 1st, 5th, or 6th position is a functional group substituted with a hetero element-containing group. The photoresist composition according to claim 2, characterized in that.

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

5. The photoresist composition according to claim 1, characterized in that the photosensitive polymer includes a first repeating unit represented by any one of the structures of Chemical Formula 1-1 below. 【Chemical Formula 1-1】 In the above Chemical Formula 1-1, R １２ 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 C6-C30 aryl group, a substituted or unsubstituted C6-C30 heteroaryl group, a substituted or unsubstituted C7-C30 arylalkyl group, or a substituted or unsubstituted phenyl group, X １２ is a non-metallic element or an anionic compound, and * is the bonding position.

6. The photoresist composition according to claim 1, characterized in that the photosensitive polymer includes a second repeating unit represented by any one of the structures of Chemical Formula 2 below. 【Chemical Formula 2】 In the chemical 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 arylalkyl group, a substituted or unsubstituted C2-C30 acetyl group, or a substituted or unsubstituted C7-C30 tosyl group, and 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 acetyl group, a substituted or unsubstituted C7-C30 tosyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 heteroaryl group, a substituted or unsubstituted C7-C30 arylalkyl group, or a substituted or unsubstituted phenyl group, and X ２１ is a non-metallic element or an anionic compound, and * is the bonding position.

7. Said R ２１ is a substituted C5-C30 alkyl group, wherein at least one hydrogen bonded to the carbon at the 1st, 5th or 6th position is substituted with a secondary or higher substituent, or a functional group in which the carbon atom at the 1st, 5th or 6th position is substituted with a hetero element-containing group. The photoresist composition according to claim 6, characterized in that.

8. Said R ２１ is a substituted or unsubstituted C5-C30 alkenyl group, and is a functional group having a double bond between the 4th carbon and the 5th carbon, between the 5th carbon and the 6th carbon, or between the 6th carbon and the 7th carbon. The photoresist composition according to claim 6, characterized in that.

9. The photoresist composition according to claim 1, characterized in that the photosensitive polymer includes a third repeating unit represented by any one of the structures of Chemical Formula 3 below. 【Chemical Formula 3】 In the chemical 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 arylalkyl group, a substituted or unsubstituted C2-C30 acetyl group, or a substituted or unsubstituted C7-C30 tosyl group, and R ３２ and R ３３ are 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 acetyl group, a substituted or unsubstituted C7-C30 tosyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 heteroaryl group, a substituted or unsubstituted C7-C30 arylalkyl group, or a substituted or unsubstituted phenyl group, X ３１ is a non-metallic element or an anionic compound, and * is the bonding position.

10. Said R ３１ is a substituted C5-C30 alkyl group, and at least one hydrogen bonded to the carbon at the 1st, 5th, or 6th position is substituted with a secondary or higher substituent, or the carbon atom at the 1st, 5th, or 6th position is a functional group substituted with a hetero element-containing group. The photoresist composition according to claim 9, characterized in that.

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