Semiconductor photoresist composition and method of forming pattern using the same

Abstract

Disclosed are a semiconductor photoresist composition and a method of forming a pattern using the same, the semiconductor photoresist composition comprising: a Sn-containing organometallic compound; a carboxylic acid compound; at least one compound selected from a sulfonic acid compound and a phosphonic acid compound; and a solvent.

Description

[0001] Cross - reference to related applications

[0002] This application claims priority and the benefit of Korean Patent Application No. 10 - 2024 - 0001129, filed with the Korean Intellectual Property Office on January 3, 2024, the entire content of which is incorporated herein by reference. Technical field

[0003] Embodiments of the present disclosure relate to a semiconductor photoresist composition and a method of forming a pattern using the same. Background art

[0004] EUV (extreme ultraviolet) lithography technology has attracted attention as a technology for manufacturing next - generation semiconductor devices. EUV lithography is a pattern - forming technology that uses EUV rays with a wavelength of 13.5 nanometers as an exposure light source. According to EUV lithography technology, extremely fine patterns (e.g., less than or equal to 20 nanometers) can be formed in the exposure process during semiconductor device manufacturing.

[0005] EUV lithography technology is achieved by developing compatible photoresists that can perform at a spatial resolution of less than or equal to 16 nanometers. Currently, efforts are being made to meet the insufficient specifications of traditional chemically amplified (CA) photoresists for next - generation devices, such as resolution, photosensitivity, and characteristic roughness (also referred to as line - edge roughness or LER).

[0006] The inherent image blur caused by the acid - catalyzed reaction in polymer - type photoresists limits the resolution of small feature sizes, which has always existed in electron - beam (e - beam) lithography. CA photoresists are designed for high sensitivity, but due to their typical elemental composition, which reduces the light absorption of the photoresist at a wavelength of 13.5 nanometers, thereby reducing their sensitivity, CA photoresists may face more difficulties in EUV exposure.

[0007] CA photoresists may face difficulties in small feature sizes due to roughness problems, and experiments show that the line - edge roughness (LER) of CA photoresists increases as the photosensitivity decreases, partly due to the characteristics of the acid - catalyzed process. Therefore, due to the above - mentioned defects and problems of CA photoresists, high - performance photoresists would be highly beneficial to the semiconductor industry.

[0008] To overcome the disadvantages of the above-described chemically amplified (CA) organic photosensitive compositions, inorganic photosensitive compositions have been studied. Inorganic photosensitive compositions are mainly used for negative patterning and have the ability to resist removal by a developer composition through chemical modification by a non-chemical amplification mechanism. Such inorganic compositions contain inorganic elements with higher EUV absorption rates than hydrocarbons, and thus can ensure sensitivity through a non-chemical amplification mechanism and may be less sensitive to random effects, resulting in low line edge roughness and a relatively small number of defects.

[0009] Inorganic photoresists based on tungsten peroxopolyacids mixed with tungsten, niobium, titanium, and / or tantalum have been reported as radiation-sensitive materials for patterning.

[0010] The above materials are effective for large-pitch patterning in a bilayer configuration for far ultraviolet (deep ultraviolet), X-ray, and electron beam light sources. Recently, impressive performance has been obtained when imaging 15-nanometer half-pitch (HP) by projection EUV exposure using a cationic hafnium metal oxide sulfate (HfSOx) material together with a peroxo complexing agent. The above system exhibits the highest performance of non-CA photoresists and has a practical photosensitivity close to the requirements of EUV photoresists. However, the hafnium metal oxide sulfate materials with peroxo complexing agents have some practical disadvantages. First, these materials are coated in a corrosive sulfuric acid / hydrogen peroxide mixture and have insufficient shelf-life stability. Second, structural changes for performance improvement as a composite mixture are not easy. Third, development should be carried out in a 25 wt% TMAH (tetramethylammonium hydroxide) solution and / or the like with extremely high concentration.

[0011] Recently, active research has been conducted on tin-containing molecules that have excellent absorption of extreme ultraviolet rays. Among them, the alkyl ligands of organotin polymers are dissociated by light absorption and / or the resulting secondary electrons and crosslinked with adjacent chains through oxygen bonds, thereby achieving negative patterning that cannot be removed by an organic developer. Such organotin polymers exhibit greatly improved sensitivity while maintaining resolution and line edge roughness, but further improvement of patterning characteristics would be beneficial for commercial availability. SUMMARY OF THE INVENTION

[0012] Some embodiments provide semiconductor photoresist compositions having excellent sensitivity and line edge roughness (LER) characteristics and improved sensitivity.

[0013] Some embodiments provide methods of forming a pattern using the semiconductor photoresist compositions.

[0014] A semiconductor photoresist composition according to some embodiments includes: a Sn-containing organometallic compound; a carboxylic acid compound; at least one compound selected from a sulfonic acid compound and a phosphonic acid compound; and a solvent.

[0015] A method of forming a pattern according to some embodiments includes: providing an etch target film on a substrate; coating a semiconductor photoresist composition on the etch target film to form a photoresist film; patterning the photoresist film to form a photoresist pattern; and etching the etch target film using the photoresist pattern as an etch mask.

[0016] A semiconductor photoresist composition according to some embodiments achieves excellent sensitivity and excellent LER characteristics. Description of the Drawings

[0017] The drawings, together with the specification, illustrate embodiments of the subject matter of the present disclosure and, together with the description, are used to explain the principles of the embodiments of the subject matter of the present disclosure.

[0018] Figures 1 - 5 is a cross-sectional view illustrating a method of forming a pattern using a semiconductor photoresist composition according to some embodiments.

[0019] Description of Reference Numerals

[0020] 100: Substrate

[0021] 102: Thin film

[0022] 104: Antireflective bottom layer

[0023] 106: Photoresist film

[0024] 106a: Exposed area

[0025] 106b: Unexposed area

[0026] 108: Photoresist pattern

[0027] 112: Organic film pattern

[0028] 110: Patterning mask

[0029] 114: Thin film pattern Detailed Description

[0030] Hereinafter, embodiments of the present disclosure will be described in more detail with reference to the drawings. In the following description of the subject matter of the present disclosure, well-known functions or structures will not be described in order to clarify the subject matter of the present disclosure.

[0031] To clearly illustrate the subject matter of the present disclosure, certain descriptions and relationships may be omitted, and throughout the disclosure, the same or similar configuration elements are designated by the same reference numerals. In addition, since the dimensions and thicknesses of each configuration shown in the drawings may be arbitrarily shown for better understanding and ease of description, the present disclosure is not necessarily limited thereto.

[0032] In the drawings, the thicknesses of layers, films, panels, regions, etc. may be exaggerated for clarity. In the drawings, the thicknesses of some layers or regions, etc. may be exaggerated for clarity. It should be understood that when an element such as a layer, film, region, or substrate is referred to as being "on" another element, it can be directly on the other element or there may also be intervening elements.

[0033] As used herein, "substituted" means that a hydrogen atom is replaced by the following: deuterium, halogen, hydroxyl, carboxyl, mercapto, cyano, nitro, -NRR' (wherein R and R' are each independently hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated cycloaliphatic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), -SiRR'R" (wherein R, R', and R" are each independently hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated cycloaliphatic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), a C1 to C30 alkyl group, a C1 to C10 haloalkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a C1 to C20 sulfide group, or a combination thereof. "Unsubstituted" means that the hydrogen atom is not replaced by other substituents and retains the hydrogen atom.

[0034] As used herein, when no other definition is provided, "alkyl" means a straight-chain or branched-chain aliphatic hydrocarbon group. An alkyl group can be a "saturated alkyl" group that does not contain any double or triple bonds.

[0035] An alkyl group can be a C1 to C8 alkyl group. For example, an alkyl group can be a C1 to C7 alkyl group, a C1 to C6 alkyl group, or a C1 to C5 alkyl group. For example, a C1 to C5 alkyl group can be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or 2,2-dimethylpropyl.

[0036] As used herein, when no other definition is provided, "cycloalkyl" means a monovalent cyclic aliphatic hydrocarbon group.

[0037] A cycloalkyl group can be a C3 to C8 cycloalkyl group, for example, a C3 to C7 cycloalkyl group, a C3 to C6 cycloalkyl group, a C3 to C5 cycloalkyl group, or a C3 to C4 cycloalkyl group. For example, a cycloalkyl group can be cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl, but is not limited thereto.

[0038] As used herein, "aliphatic unsaturated organic group" means a hydrocarbon group in which the bond between one carbon atom and another carbon atom in the indicated molecule is a double bond, a triple bond, or a combination thereof.

[0039] The aliphatic unsaturated organic group may be a C2 to C8 aliphatic unsaturated organic group. For example, the aliphatic unsaturated organic group may be a C2 to C7 aliphatic unsaturated organic group, a C2 to C6 aliphatic unsaturated organic group, a C2 to C5 aliphatic unsaturated organic group, or a C2 to C4 aliphatic unsaturated organic group. For example, the C2 to C4 aliphatic unsaturated organic group may be vinyl, ethynyl, allyl, 1-propenyl, 1-methyl-1-propenyl, 2-propenyl, 2-methyl-2-propenyl, 1-propynyl, 1-methyl-1-propynyl, 2-propynyl, 2-methyl-2-propynyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-butynyl, 2-butynyl, or 3-butynyl.

[0040] As used herein, "aryl" refers to a substituent in which all atoms (or all ring atoms, e.g., all ring atoms except hydrogen and / or other substituents) in the cyclic substituent have p orbitals and these p orbitals are conjugated, and may include monocyclic or fused-ring polycyclic functional groups (e.g., rings sharing adjacent carbon atom pairs).

[0041] As used herein, "heteroaryl" refers to an aryl containing at least one heteroatom selected from N, O, S, P, and Si. Two or more heteroaryls are directly connected by a σ bond, or when the heteroaryl contains two or more rings, two or more rings may be fused together. When the heteroaryl is a fused ring, each ring may contain one to four heteroatoms.

[0042] As used herein, unless otherwise defined, "alkenyl" refers to an aliphatic unsaturated alkenyl of a straight-chain or branched-chain aliphatic hydrocarbon group containing at least one double bond.

[0043] As used herein, unless otherwise defined, "alkynyl" refers to an aliphatic unsaturated alkynyl of a straight-chain or branched-chain aliphatic hydrocarbon group containing at least one triple bond.

[0044] The following describes a semiconductor photoresist composition according to some embodiments.

[0045] A semiconductor photoresist composition according to some embodiments includes: an organometallic compound containing Sn; a carboxylic acid compound; at least one compound selected from a sulfonic acid compound and a phosphonic acid compound; and a solvent.

[0046] The semiconductor photoresist composition can improve sensitivity and LER and achieve excellent resolution by containing at least two types (or kinds) of acid compounds, such as a carboxylic acid compound and at least one compound selected from a sulfonic acid compound and a phosphonic acid compound.

[0047] As an example, the carboxylic acid compound: at least one compound selected from a sulfonic acid compound and a phosphonic acid compound may be included in a weight ratio of about 1:0.001 to about 1:10.

[0048] As an example, the carboxylic acid compound and at least one compound selected from sulfonic acid compounds and phosphonic acid compounds may be included at a weight ratio of about 1:0.01 to about 1:7.

[0049] The carboxylic acid compound may be represented by Chemical Formula 1.

[0050] Chemical Formula 1

[0051]

[0052] In Chemical Formula 1,

[0053] R 1 is amino, halogen, hydroxy, carboxy, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C7-C30 aralkyl,

[0054] L 1 and L 2 each independently is a single bond (e.g., a single covalent bond), substituted or unsubstituted C1-C20 alkylene, substituted or unsubstituted C6-C30 arylene or a combination thereof,

[0055] X 1 is a single bond (e.g., a single covalent bond), O, S or NR 2 (wherein R 2 is hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl or a combination thereof), and

[0056] m1 is an integer greater than or equal to 1.

[0057] The upper limit of m1 may be the maximum value that can be connected to L 2 but m1 may be, for example, 1 to 10, 1 to 8, 1 to 6 or 1 to 3 within a range lower than the maximum value.

[0058] The sulfonic acid compound may be represented by Chemical Formula 2.

[0059] Chemical Formula 2

[0060]

[0061] In Chemical Formula 2,

[0062] R 3is amino, halogen, hydroxyl, carboxyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C7-C30 aralkyl,

[0063] L 3 and L 4 each independently is a single bond (e.g., a single covalent bond), substituted or unsubstituted C1-C20 alkylene, substituted or unsubstituted C6-C30 arylene or a combination thereof,

[0064] X 2 is a single bond (e.g., a single covalent bond), O, S or NR 4 (wherein R 4 is hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl or a combination thereof), and

[0065] m2 is an integer greater than or equal to 1.

[0066] The upper limit of m2 can be the maximum value that can be connected to L 4 but m2 can be, for example, 1 to 10, 1 to 8, 1 to 6 or 1 to 3 within a range lower than the maximum value.

[0067] The phosphonic acid compound can be represented by Chemical Formula 3.

[0068] Chemical Formula 3

[0069]

[0070] In Chemical Formula 3,

[0071] R 5 is amino, halogen, hydroxyl, carboxyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C7-C30 aralkyl,

[0072] L 5 and L 6 each independently is a single bond (e.g., a single covalent bond), substituted or unsubstituted C1-C20 alkylene, substituted or unsubstituted C6-C30 arylene or a combination thereof,

[0073] X 3 is a single bond (e.g., a single covalent bond), O, S, or NR 6 (R 6 is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), and

[0074] m3 is an integer greater than or equal to 1.

[0075] The upper limit of m3 can be the maximum value that can be attached to L 6 but m3 can be, for example, in the range of 1 to 10, 1 to 8, 1 to 6, or 1 to 3 below the maximum value.

[0076] For example, R 1 , R 3 and R 5 can each independently be a hydroxyl group, a carboxyl group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted benzyl group.

[0077] For example, L 1 to L 6 can each independently be a single bond (e.g., a single covalent bond), a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, a substituted or unsubstituted pentylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group.

[0078] As an example, the carboxylic acid compound can be one of the compounds listed in Group 1.

[0079] Group 1

[0080]

[0081] As an example, the sulfonic acid compound and the phosphonic acid compound can be one of the compounds listed in Group 2.

[0082] Group 2

[0083]

[0084] Based on 100% by weight of the semiconductor photoresist composition, it may include a carboxylic acid compound in an amount of 0.001 to 10% by weight and at least one compound selected from a sulfonic acid compound and a phosphonic acid compound.

[0085] For example, based on 100% by weight of the semiconductor photoresist composition, it may include a carboxylic acid compound in an amount of about 0.01 to about 10% by weight, about 0.01 to about 5% by weight, about 0.05 to about 5% by weight, or about 0.1 to about 5% by weight and at least one compound selected from a sulfonic acid compound and a phosphonic acid compound.

[0086] Based on 100% by weight of the semiconductor photoresist composition, it may include an organometallic compound containing Sn in an amount of about 0.5% by weight to about 30% by weight.

[0087] The semiconductor photoresist composition according to some embodiments can improve the sensitivity of the photoresist by containing an organometallic compound containing Sn, a carboxylic acid compound, and at least one compound selected from a sulfonic acid compound and a phosphonic acid compound within the above content ranges.

[0088] The semiconductor photoresist composition according to some embodiments may contain an organometallic compound containing Sn: a carboxylic acid compound and at least one compound selected from a sulfonic acid compound and a phosphonic acid compound in a weight ratio of about 99:1 to about 80:20. For example, the semiconductor photoresist composition may contain an organometallic compound containing Sn: a carboxylic acid compound and at least one compound selected from a sulfonic acid compound and a phosphonic acid compound in a weight ratio of about 99:1 to about 90:10.

[0089] If the weight ratio of the organometallic compound containing Sn and the acid compound satisfies the above range, a semiconductor photoresist composition with excellent sensitivity can be provided.

[0090] The organometallic compound containing Sn may include at least one selected from an organic oxy group and an organic carbonyl oxy group.

[0091] The organometallic compound may be a compound represented by Chemical Formula 4 and / or its condensation compound.

[0092] Chemical Formula 4

[0093]

[0094] In Chemical Formula 4,

[0095] R 7Selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C6-C30 aralkyl,

[0096] R 8 to R 10 each independently is substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aralkyl, alkoxy, and aryloxy (-OR a , where R a is substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, or a combination thereof), carboxyl (-O(CO)R b , where R b is hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, or a combination thereof), alkylamino and / or dialkylamino (-NR c R d , where R c and R d each independently is hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, or a combination thereof), amido (-NR e (COR f ), where R e and R f each independently is hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, or a combination thereof), amidino (-NR g C(NR h )R i , where R g , R h and Ri each independently is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof), an alkylthio group and / or an arylthio group (-SR j , wherein R j is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof) and / or a thiocarboxyl group (-S(CO)R k , wherein R k is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof),

[0097] R 8 to R 10 at least one of which is selected from: an alkoxy group and an aryloxy group (-OR a , wherein R a is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof), a carboxyl group (-O(CO)R b , wherein R b is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof), an alkylamino group and / or a dialkylamino group (-NR c R d , wherein R c and R d each independently is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof), an amide group (-NR e (COR f ), wherein R e and R fEach independently is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof), an amidino group (-NR g C(NR h )R i , wherein R g , R h and R i each independently is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof), an alkylthio group and an arylthio group (-SR j , wherein R j is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof) and a thiocarboxyl group (-S(CO)R k , wherein R k is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof).

[0098] R 8 to R 10 at least one of which is optionally selected from: an alkoxy group and an aryloxy group (-OR a , wherein R a is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof) and a carboxyl group (-O(CO)R b , wherein R b is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof).

[0099] In the examples, the compound represented by Chemical Formula 4 includes -OR a and / or -OC(=O)Rb As a ligand, the pattern formed using a semiconductor photoresist composition containing the same can exhibit excellent ultimate resolution.

[0100] In an embodiment, -OR a and / or -OC(=O)R b The ligand can determine the solubility of the compound represented by Chemical Formula 4 in a solvent.

[0101] R 7 may be a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C4 to C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof,

[0102] R a may be a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, and

[0103] R b may be hydrogen, a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.

[0104] R 7 may be methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, formyl, acetyl, propionyl, butyryl, valeryl, ethoxy, propoxy, or a combination thereof,

[0105] R a may be ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or a combination thereof, and

[0106] R bIt can be hydrogen, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl or a combination thereof.

[0107] In the examples, the Sn-containing organometallic compound can be represented by Chemical Formula 5 or Chemical Formula 6.

[0108] Chemical Formula 5

[0109] R 11 z SnO (2-(z / 2)-(x / 2)) (OH) x

[0110] In Chemical Formula 5,

[0111] R 11 is a C1-C31 hydrocarbon group, where 0 < z ≤ 2 and 0 < (z + x) ≤ 4;

[0112] Chemical Formula 6

[0113] R 12 a1 Sn b1 X c1 Y d1

[0114] Among them, in Chemical Formula 6,

[0115] R 12 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C4-C30 heteroaryl group, a carbonyl group, an epoxyethyl group, an epoxypropyl group or a combination thereof,

[0116] X is sulfur (S), selenium (Se) or tellurium (Te),

[0117] Y is -OR l or -OC(=O)R m ,

[0118] where R l is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof,

[0119] R mis hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, and

[0120] a1, b1, c1, and d1 are each independently an integer in the range of 1 to 20.

[0121] According to some embodiments, the solvent of the semiconductor photoresist composition may be an organic solvent, for example, it may be an aromatic compound (such as xylene, toluene, etc.), alcohols (such as 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropanol, 1-propanol), ethers (such as anisole, tetrahydrofuran), esters (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate), ketones (such as methyl ethyl ketone, 2-heptanone), or a mixture thereof, but not limited thereto.

[0122] According to some embodiments, in addition to the above-mentioned Sn-containing organometallic compound, acid compound, and solvent, the semiconductor photoresist composition may further include a resin.

[0123] The resin may be a phenolic resin containing at least one aromatic moiety of Group 3.

[0124] Group 3

[0125]

[0126] The resin may have a weight average molecular weight of about 500 to about 20,000.

[0127] Based on the total amount of the semiconductor photoresist composition, the resin may be included in an amount of about 0.1 wt% to about 50 wt%.

[0128] If the resin is included within the above content range, it may have excellent etching resistance and heat resistance.

[0129] In an embodiment, the semiconductor photoresist composition may be composed of the above-mentioned Sn-containing organometallic compound, acid compound, solvent, and resin.

[0130] However, the semiconductor photoresist composition according to the above embodiments may further include additives as needed or required. Examples of additives may be surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or a combination thereof.

[0131] The surfactant may include, for example, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycols, quaternary ammonium salts, or a combination thereof, but not limited thereto.

[0132] The crosslinking agent can be, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, an acrylic crosslinking agent, an epoxy crosslinking agent, and / or a polymer-based crosslinking agent, but is not limited thereto. The crosslinking agent can have at least two substituents that form crosslinks. For example, compounds and / or analogs such as methoxymethylated biuret, butoxymethylated biuret, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, methyl methacrylate, 1,4-butanediol diglycidyl ether, glycidol, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, trimethylolpropane triglycidyl ether, 1,3-bis(glycidyloxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea.

[0133] The leveling agent can be used to improve the flatness of the coating during the printing process and can be any suitable leveling agent commonly used in the art.

[0134] The organic acid can include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, fluorinated sulfonium salts, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or a combination thereof, but is not limited thereto.

[0135] The quencher can be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0136] The usage amount of the additive can be controlled according to suitable or desired properties.

[0137] In the examples, the semiconductor photoresist composition can further include a silane coupling agent as an adhesion enhancer to improve the close contact force with the substrate (for example, to improve the adhesion of the semiconductor photoresist composition to the substrate). The silane coupling agent can be, for example, a silane compound containing a carbon-carbon unsaturated bond, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane; and / or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; trimethoxy[3-(phenylamino)propyl]silane, and / or analogs, but is not limited thereto.

[0138] A semiconductor photoresist composition can form a pattern with a high aspect ratio without collapse. Thus, in order to form a fine pattern having a width of, for example, about 5 nm to about 100 nm, such as about 5 nm to about 80 nm, such as about 5 nm to about 70 nm, such as about 5 nm to about 50 nm, such as about 5 nm to about 40 nm, such as about 5 nm to about 30 nm, or such as about 5 nm to about 20 nm, the semiconductor photoresist composition can be used in a lithography process using light having a wavelength range of about 5 nm to about 150 nm, such as about 5 nm to about 100 nm, about 5 nm to about 80 nm, about 5 nm to about 50 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm. Thus, the semiconductor photoresist composition according to some embodiments can be used to implement extreme ultraviolet lithography using an EUV light source having a wavelength of about 13.5 nm.

[0139] According to some embodiments, there is provided a method of forming a pattern using the above-described semiconductor photoresist composition. For example, the fabricated pattern can be a photoresist pattern.

[0140] The method of forming a pattern according to some embodiments includes: forming an etching target film on a substrate, coating a semiconductor photoresist composition on the etching target film to form a photoresist film, patterning the photoresist film to form a photoresist pattern, and etching the etching target film using the photoresist pattern as an etching mask.

[0141] The method of forming a pattern according to some embodiments includes: forming an etching target film on a substrate, coating a semiconductor photoresist composition on the etching target film to form a photoresist film, patterning the photoresist film to form a photoresist pattern, and etching the etching target film using the photoresist pattern as an etching mask.

[0142] The following refers to Figures 1 - 5 Describe a method of forming a pattern using a semiconductor photoresist composition. Figures 1 - 5 is a cross-sectional view for explaining a method of forming a pattern using a semiconductor photoresist composition according to some embodiments.

[0143] Refer to Figure 1 , prepare an object to be etched. The object to be etched can be a thin film 102 on a semiconductor substrate 100. Hereinafter, the object to be etched is defined as the thin film 102, but the present disclosure is not limited thereto. The surface of the thin film 102 is washed to remove impurities and / or the like remaining thereon. The thin film 102 can be, for example, a silicon nitride layer, a polysilicon layer, and / or a silicon oxide layer.

[0144] Subsequently, the underlayer resist composition for forming the underlayer resist 104 is coated on the surface of the washing film 102 by spin coating. However, this embodiment is not limited thereto, and various suitable coating methods can be used, such as spraying, dip coating, blade coating, printing methods (such as inkjet printing and / or screen printing), and / or the like.

[0145] The coating process of the underlayer resist can be omitted, and the following description includes the process of coating the underlayer resist.

[0146] Then, the coated composition is dried and baked to form the underlayer resist 104 on the film 102. The baking can be carried out at a temperature of about 100 °C to about 500 °C, for example, about 100 °C to about 300 °C.

[0147] The underlayer resist 104 is located between the substrate 100 and the photoresist film 106. Therefore, when the light reflected from the interface between the substrate 100 and the photoresist film 106 and / or the interlayer hard mask scatters into the unintended photoresist area, it can improve the pattern formation of the photoresist line width and prevent or reduce non-uniformity.

[0148] Refer to Figure 2 , the photoresist film 106 is formed by coating a semiconductor photoresist composition on the underlayer resist 104. The photoresist film 106 is obtained by coating the above-mentioned semiconductor photoresist composition on the film 102 on the substrate 100 and then curing it by heat treatment.

[0149] In the embodiment, forming a pattern using the semiconductor photoresist composition may include coating the semiconductor photoresist composition on the substrate 100 having the film 102 by spin coating, slot coating, inkjet printing, and / or the like, and then drying to form the photoresist film 106.

[0150] The semiconductor photoresist composition has been described in detail and will not be described again.

[0151] Subsequently, the substrate 100 having the photoresist film 106 is subjected to a first baking process. The first baking process can be carried out at a temperature of about 80 °C to about 120 °C.

[0152] Refer to Figure 3 , the photoresist film 106 can be selectively exposed using the patterning mask 110.

[0153] For example, the exposure can use actinic radiation including light having a high energy wavelength, such as EUV (extreme ultraviolet; wavelength of about 13.5 nm), E-Beam (electron beam), and / or the like, as well as light having a wavelength such as i-line (wavelength of about 365 nm), KrF excimer laser (wavelength of about 248 nm), ArF excimer laser (wavelength of about 193 nm), and / or the like.

[0154] In an embodiment, the exposure light according to some embodiments may have a short wavelength and a high energy wavelength in the range of about 5 nanometers to about 150 nanometers. For example, EUV (extreme ultraviolet; wavelength 13.5 nanometers), E-Beam (electron beam), and / or the like.

[0155] The exposed area 106a of the photoresist film 106 has a different solubility from the unexposed area 106b of the photoresist film 106 by forming a polymer, which is formed by a crosslinking reaction such as a condensation reaction between organometallic compounds.

[0156] Subsequently, a second baking process is performed on the substrate 100. The second baking process can be performed at a temperature of about 90°C to about 200°C. Due to the second baking process, the exposed area 106a of the photoresist film 106 becomes insoluble in the developer.

[0157] In Figure 4 , a developer is used to dissolve and remove the unexposed area 106b of the photoresist film to form a photoresist pattern 108. For example, the unexposed area 106b of the photoresist film is dissolved and removed by using an organic solvent such as 2-heptanone and / or the like to complete the photoresist pattern 108 corresponding to a negative image.

[0158] As described above, the developer used in the method of forming a pattern according to some embodiments may be an organic solvent. The organic solvent used in the method of forming a pattern according to some embodiments may be, for example, ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, and / or the like, alcohols such as 4-methyl-2-pentanol, 1-butanol, isopropyl alcohol, 1-propanol, methanol, and / or the like, esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, and / or the like, aromatic compounds such as benzene, xylene, toluene, and / or the like, or a combination thereof.

[0159] However, the photoresist pattern according to some embodiments is not limited to a negative image, and may be formed to have a positive image. Here, the developer for forming a positive image may be a quaternary ammonium hydroxide composition such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or a combination thereof.

[0160] As described above, exposure to light having high energy, such as EUV (extreme ultraviolet; wavelength 13.5 nm), E-Beam (electron beam), and / or the like, and light having a relatively long wavelength, such as i-line (wavelength of about 365 nm), KrF excimer laser (wavelength of about 248 nm), ArF excimer laser (wavelength of about 193 nm), and / or the like, can provide a photoresist pattern 108 having a width of about 5 nm to about 100 nm. For example, the photoresist pattern 108 can have a width of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm.

[0161] In an embodiment, the photoresist pattern 108 can have a pitch of less than or equal to about 50 nm (e.g., less than or equal to about 40 nm, e.g., less than or equal to about 30 nm, e.g., less than or equal to about 20 nm, or e.g., less than or equal to about 15 nm), and a line width roughness of less than or equal to about 10 nm, less than or equal to about 5 nm, less than or equal to about 3 nm, or less than or equal to about 2 nm.

[0162] In an embodiment, the photoresist pattern 108 is used as an etch mask to etch the underlying resist 104. Through this etching process, an organic film pattern 112 is formed. The organic film pattern 112 can also have a width corresponding to that of the photoresist pattern 108.

[0163] Referring Figure 5 , the exposed thin film 102 is etched by applying the photoresist pattern 108 as an etch mask. As a result, the thin film is formed into a thin film pattern 114.

[0164] The etching of the thin film 102 can be, for example, dry etching using an etching gas, and the etching gas can be, for example, CHF3, CF4, Cl2, BCl3, or a mixed gas thereof.

[0165] In the exposure process, the thin film pattern 114 formed using the photoresist pattern 108 formed by an exposure process performed using an EUV light source can have a width corresponding to that of the photoresist pattern 108. For example, the thin film pattern 114 can have a width of 5 nm to 100 nm equal to that of the photoresist pattern 108. For example, the thin film pattern 114 formed using the photoresist pattern 108 formed by an exposure process performed using an EUV light source can have a width of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm, or e.g., a width of less than or equal to about 20 nm, like the width of the photoresist pattern 108.

[0166] Hereinafter, embodiments of the present disclosure will be described in more detail by way of examples of the preparation of the above semiconductor photoresist composition. However, the present disclosure is not technically limited by the following examples.

[0167] Synthesis of Organometallic Compounds

[0168] Synthesis Example 1

[0169] In a 250 mL two-necked round-bottom flask, 40.7 g of tert-butyltriphenyltin and 300 g of propionic acid were added, and then heated under reflux for 24 hours.

[0170] The unreacted propionic acid was removed under reduced pressure to obtain a compound represented by Chemical Formula 7.

[0171] Chemical Formula 7

[0172]

[0173] Synthesis Example 2

[0174] In a 1 L round-bottom flask, 18.9 g of isopropyltris(diethylamino)tin was dissolved in 500 mL of anhydrous hexane. The flask was cooled to -78 °C, and then 9.0 g of isopropyl alcohol was slowly added dropwise, and the reaction was carried out at room temperature for 24 hours. After the reaction was completed, the resulting product was concentrated and dried under vacuum to obtain a compound represented by Chemical Formula 8.

[0175] Chemical Formula 8

[0176]

[0177] Synthesis Example 3

[0178] 10 g of dibutyltin dichloride was dissolved in 30 mL of diethyl ether, 70 mL of 1 M aqueous sodium hydroxide (NaOH) solution was added thereto, and then stirred for 1 hour. After stirring, the resulting solid was filtered, washed three times with 25 mL of deionized water, and dried under reduced pressure at 100 °C to obtain an organometallic compound represented by Chemical Formula 9, having a weight-average molecular weight of 1,500.

[0179] Chemical Formula 9

[0180]

[0181] Preparation of Semiconductor Photoresist Composition

[0182] Examples 1 to 9 and Comparative Examples 1 to 3

[0183] The organometallic compounds, carboxylic acid compounds, and phosphonic acid compounds represented by Chemical Formulas 7 to 9 in Synthesis Examples 1 to 3 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) at the respective weight ratios shown in Table 1 at a concentration of 3% by weight, and then filtered through a 0.1-μm PTFE (polytetrafluoroethylene) syringe filter to prepare a semiconductor photoresist composition.

[0184] Table 1

[0185]

[0186]

[0187] C1: Propionic acid

[0188] P1: 3-Phosphonopropionic acid

[0189] S1: 3-Hydroxypropane-1-sulfonic acid

[0190] Evaluation 1: Evaluation of sensitivity and line edge roughness (LER)

[0191] Each semiconductor photoresist composition in the examples and comparative examples was spin-coated on a 200-mm circular silicon wafer with hexamethyldisilane (HMDS) deposited on the surface at a speed of 1500 revolutions per minute for 30 seconds, baked at 110 °C (post-apply baked, PAB) for 60 seconds, and then left standing at room temperature (23 ± 2 °C) for 30 seconds.

[0192] Subsequently, a line array composed of 50 circular pads, each with a diameter of 500 μm, was projected onto the wafer coated with the photoresist composition using extreme ultraviolet light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). Here, the exposure time of the pads was adjusted to apply an increasing extreme ultraviolet dose to each pad.

[0193] Subsequently, the resist and the substrate were exposed on a hot plate at 160 °C for 120 seconds and then baked. The baked film was developed with a PGMEA solvent to form a negative image. Finally, it was baked on a hot plate at 150 °C for 2 minutes to complete the process.

[0194] The remaining resist thickness of the exposed pads was measured using an ellipsometer. The sensitivity was measured by measuring the remaining thickness at each exposure dose and plotting it as a function of the exposure dose, and the LER (line edge roughness) was measured from the field emission scanning electron microscope (FE-SEM) image. The sensitivity and line edge roughness were evaluated according to the following criteria, and the results are shown in Table 2.

[0195] Sensitivity evaluation criteria

[0196] -A: Less than 16 mJ / cm 2

[0197] -B: Greater than or equal to 16 mJ / cm 2

[0198] LER evaluation criteria

[0199] -○: Less than or equal to 2 nm

[0200] -△: Greater than 2 nm and less than or equal to 5 nm

[0201] -X: Greater than 5 nm

[0202] Evaluation 2: Evaluation of resolution (CD)

[0203] After the process is completed, a line / space CD pattern is formed on the patterned wafer, and then it is transferred to a CD-SEM measurement device (GC-9380, Hitachi) to measure the CD (critical dimension) size of the region where the mask pattern half pitch is 14 nm, and the minimum value of the space CD, which is the distance between the lines, is shown in Table 2.

[0204] Table 2

[0205]

[0206]

[0207] From the results in Table 2, it can be seen that the patterns formed using the semiconductor photoresist compositions of Examples 1 to 9 exhibit superior sensitivity, LER, and resolution characteristics compared to the patterns formed using the semiconductor photoresist compositions of Comparative Examples 1 to 3.

[0208] Prior to this, exemplary embodiments of the present invention have been described and illustrated. However, it should be apparent to those of ordinary skill in the art that the present disclosure is not limited to the described embodiments, and various modifications and conversions can be made without departing from the spirit and scope of the present disclosure. Therefore, such modified or converted embodiments should not be understood separately from the technical ideas and aspects of the present disclosure, and the modified embodiments are within the scope of the appended claims and their equivalents.

Claims

1. A semiconductor photoresist composition, comprising: a Sn-containing organometallic compound; a carboxylic acid compound; at least one compound selected from a sulfonic acid compound and a phosphonic acid compound; and a solvent.

2. The semiconductor photoresist composition according to claim 1, wherein: the carboxylic acid compound and the at least one compound selected from the sulfonic acid compound and the phosphonic acid compound are included in a weight ratio of 1:0.001 to 1:

10.

3. The semiconductor photoresist composition according to claim 1, wherein: the carboxylic acid compound is represented by Chemical Formula 1: Chemical Formula 1 wherein, in Chemical Formula 1, R 1 is an amino group, a halogen, a hydroxyl group, a carboxyl group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C7-C30 aralkyl group, L 1 and L 2 each independently is a single bond, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C6-C30 arylene group, or a combination thereof X 1 is a single bond, O, S, or NR 2 , where R 2 is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group or a combination thereof, and m1 is an integer greater than or equal to 1.

4. The semiconductor photoresist composition according to claim 1, wherein: the sulfonic acid compound is represented by Chemical Formula 2: Chemical Formula 2 wherein, in Chemical Formula 2, R 3 is an amino group, a halogen, a hydroxyl group, a carboxyl group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C7-C30 aralkyl group, L 3 and L 4 each independently is a single bond, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C6-C30 arylene group, or a combination thereof X 2 is a single bond, O, S, or NR 4 , where R 4 is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof, and m2 is an integer greater than or equal to 1.

5. The semiconductor photoresist composition according to claim 1, wherein: the phosphonic acid compound is represented by Chemical Formula 3: Chemical Formula 3 wherein, in Chemical Formula 3, R 5 is an amino group, a halogen, a hydroxyl group, a carboxyl group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C7-C30 aralkyl group, L 5 and L 6 each independently is a single bond, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C6-C30 arylene group, or a combination thereof, X 3 is a single bond, O, S, or NR 6 , wherein R 6 is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group or a combination thereof, and m3 is an integer greater than or equal to 1.

6. The semiconductor photoresist composition according to claim 1, wherein the carboxylic acid compound is at least one compound selected from the compounds listed in Group 1: Group 1 7. The semiconductor photoresist composition according to claim 1, wherein: the sulfonic acid compound and the phosphonic acid compound are at least one compound selected from the compounds listed in Group 2: Group 2 8. The semiconductor photoresist composition according to claim 1, wherein: based on 100% by weight of the semiconductor photoresist composition, the carboxylic acid compound and the at least one compound selected from the sulfonic acid compound and the phosphonic acid compound are included in an amount of 0.001 to 10% by weight.

9. The semiconductor photoresist composition according to claim 1, wherein: based on 100% by weight of the semiconductor photoresist composition, the carboxylic acid compound and the at least one compound selected from the sulfonic acid compound and the phosphonic acid compound are included in an amount of 0.1 to 5% by weight.

10. The semiconductor photoresist composition according to claim 1, wherein: based on 100% by weight of the semiconductor photoresist composition, the Sn-containing organometallic compound is included in an amount of 0.5% to 30% by weight.

11. The semiconductor photoresist composition according to claim 1, wherein: the semiconductor photoresist composition further comprises: additives such as a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quenching agent, or a combination thereof.

12. The semiconductor photoresist composition according to claim 1, wherein: the Sn-containing organometallic compound includes at least one selected from an organic oxy group and an organic carbonyl oxy group.

13. The semiconductor photoresist composition according to claim 1, wherein: the Sn-containing organometallic compound is a compound represented by Chemical Formula 4 or a condensation compound thereof: Chemical Formula 4 wherein, in Chemical Formula 4, R 7 selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C6-C30 aralkyl R 8 to R 10 are each independently a substituted or unsubstituted C1-C20 alkyl group; a substituted or unsubstituted C3-C20 cycloalkyl group; a substituted or unsubstituted C2-C20 alkenyl group; a substituted or unsubstituted C2-C20 alkynyl group; a substituted or unsubstituted C6-C30 aryl group; a substituted or unsubstituted C6-C30 aralkyl group; an alkoxy group and / or an aryloxy group represented by -OR a wherein R a is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof; a carboxyl group represented by -O(CO)R b wherein R b is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof; an alkylamino group and / or a dialkylamino group represented by -NR c R d wherein R c and R d are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof; an amide group represented by -NR e (COR f ) wherein R e and R f are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof; an amidino group represented by -NR g C(NR h )R i wherein R g , R h and R i are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof; an alkylthio group represented by -SR j An alkylthio group and / or an arylthio group represented by R j is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof; and / or a thiocarboxyl group represented by -S(CO)R k wherein R k is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof, R 8 to R 10 at least one selected from: alkoxy and aryloxy represented by -OR a wherein R a is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof; carboxy represented by -O(CO)R b wherein R b is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof; alkylamino and dialkylamino represented by -NR c R d wherein R c and R d are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof; amido represented by -NR e (COR f ) wherein R e and R f are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof; amidino represented by -NR g C(NR h )R i wherein R g , R h and R i are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof; alkylthio and arylthio represented by -SR j wherein R j is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof; and a thiocarboxyl group represented by -S(CO)R k wherein R k is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof.

14. The semiconductor photoresist composition according to claim 13, wherein: R 8 to R 10 at least one selected from: alkoxy and aryloxy represented by -OR a wherein R a is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof; and carboxy represented by -O(CO)R b wherein R b is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof.

15. The semiconductor photoresist composition according to claim 13, wherein: R 7 is a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C4-C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group or a combination thereof, R a is a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group or a combination thereof, and R b is hydrogen, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

16. The semiconductor photoresist composition according to claim 1, wherein: The Sn-containing organometallic compound is represented by Chemical Formula 5 or Chemical Formula 6: Chemical Formula 5 R 11 z SnO (2-(z / 2)-(x / 2)) (OH) x wherein, in Chemical Formula 5, R 11 is a C1 to C31 hydrocarbon group, where 0 < z ≤ 2 and 0 < (z + x) ≤ 4; Chemical Formula 6 R 12 a1 Sn b1 X c1 Y d1 wherein, in Chemical Formula 6, R 12 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C4-C30 heteroaryl group, a carbonyl group, an oxiranyl group, an oxetanyl group, or a combination thereof, X is sulfur, selenium or tellurium, Y is -OR l or -OC(=O)R m , wherein R l is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof, R m is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof, and a1, b1, c1 and d1 are each independently an integer from 1 to 20.

17. A method of forming a pattern, comprising: disposing an etching target film on a substrate; coating the semiconductor photoresist composition according to any one of claims 1 to 16 on the etching target film to form a photoresist film; patterning the photoresist film to form a photoresist pattern; and etching the etching target film using the photoresist pattern as an etching mask.

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