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 including a Sn-containing organometallic compound, a compound represented by Chemical Formula 1, and a solvent. The chemical formula 1 is described in the specification.

Description

[0001] Cross - reference to related applications

[0002] This application claims the priority and benefit of Korean Patent Application No. 10 - 2024 - 0001135, 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 composition. Background art

[0004] EUV (extreme ultraviolet) lithography is regarded 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, extremely fine patterns (e.g., less than or equal to 20 nanometers) can be formed in the exposure process during semiconductor device manufacturing.

[0005] Extreme ultraviolet (EUV) lithography can be achieved by developing compatible photoresists capable of performing 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 known as line - edge roughness or LER).

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

[0007] CA photoresists may encounter difficulties with small feature sizes due to roughness problems, and experiments show that the line - edge roughness (LER) of CA photoresists increases as the photosensitivity decreases, which is at least partly due to the nature of the acid - catalyzed process. Therefore, due to these defects and problems of CA photoresists, high - performance photoresists would be beneficial to the semiconductor industry.

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

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

[0010] These 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 if a cationic hafnium metal oxide sulfate (HfSOx) material is used with a peroxo complexing agent for imaging 15-nanometer half-pitch (HP) through projection EUV exposure. The system exhibits the highest performance of non-CA photoresists and has a practical photosensitivity close to or suitable for EUV photoresist requirements. However, 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 light. Among them, the alkyl ligands of organotin polymers dissociate through light absorption or the resulting secondary electrons and crosslink with adjacent chains through oxygen bonds, thus achieving negative patterning that cannot be removed by organic developers. Such organotin polymers exhibit greatly improved sensitivity while maintaining resolution and line edge roughness, but for commercial availability, patterning characteristics still need to be further improved. Summary of the Invention

[0012] Some embodiments of the present disclosure provide a semiconductor photoresist composition having excellent sensitivity characteristics.

[0013] Some embodiments provide a method of forming a pattern using the semiconductor photoresist composition.

[0014] The semiconductor photoresist composition according to some embodiments includes a Sn-containing organometallic compound; a compound represented by Chemical Formula 1; and a solvent.

[0015] [Chemical Formula 1]

[0016]

[0017] In Chemical Formula 1,

[0018] R 1 is an unsubstituted C3 to C10 alkylene group, a substituted C1 to C10 alkylene group, a substituted or unsubstituted C4 to C20 cycloalkylene group, a substituted or unsubstituted C4 to C20 cycloalkenylene group, a substituted or unsubstituted C3 to C5 alkenylene group, a substituted or unsubstituted C3 to C5 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroalkylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof.

[0019] A method of forming a pattern according to some embodiments includes forming an etch target layer on a substrate, coating a semiconductor photoresist composition on the etch target layer to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and etching the etch target layer using the photoresist pattern as an etch mask.

[0020] A semiconductor photoresist composition according to some embodiments can achieve excellent sensitivity and LER characteristics. Description of the Drawings

[0021] 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.

[0022] Figures 1A - 1E is a cross-sectional view illustrating a method of forming a pattern using a semiconductor photoresist composition according to some embodiments.

[0023] Description of the Reference Numerals

[0024] 100: Substrate

[0025] 102: Thin film

[0026] 104: Antireflective bottom layer

[0027] 106: Photoresist layer

[0028] 106a: Unexposed area

[0029] 106b: Exposed area

[0030] 108: Photoresist pattern

[0031] 112: Organic layer pattern

[0032] 110: Patterning mask

[0033] 114: Thin film pattern Detailed Description

[0034] Hereinafter, embodiments will be described in more detail with reference to the accompanying 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 description of the embodiments of the present disclosure.

[0035] To clearly illustrate the embodiments 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.

[0036] 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 if an element such as a layer, film, region, or substrate is referred to as "on" another element, it may be directly on the other element or there may also be intervening elements therebetween.

[0037] As used herein, "substituted" means that a hydrogen atom is replaced by the following: deuterium, halogen, hydroxyl, 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.

[0038] As used herein, if no other definition is provided, "alkyl" means a straight-chain or branched-chain aliphatic hydrocarbon group. The alkyl group can be a "saturated alkyl group" that does not contain any double bonds or triple bonds.

[0039] The alkyl group can be a C1 to C8 alkyl group. For example, the 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, the C1 to C5 alkyl group can be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or 2,2-dimethylpropyl.

[0040] As used herein, if no other definition is provided, "cycloalkyl" means a monovalent cyclic aliphatic saturated hydrocarbon group.

[0041] The cycloalkyl group can be a C3 to C8 cycloalkyl group, for example, a C3 to C7 cycloalkyl group or a C3 to C6 cycloalkyl group. For example, the cycloalkyl group can be cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, but is not limited thereto.

[0042] As used herein, "aliphatic unsaturated organic group" refers to a hydrocarbon group in which the bonds between carbon atoms in the molecule are double bonds, triple bonds or a combination thereof.

[0043] The aliphatic unsaturated organic group can be a C2 to C8 aliphatic unsaturated organic group. For example, the aliphatic unsaturated organic group can 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 can 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.

[0044] As used herein, "aryl" refers to a substituent in which all atoms in the cyclic substituent have p orbitals and these p orbitals are conjugated, and can include monocyclic or fused polycyclic functional groups (i.e., rings sharing adjacent carbon atom pairs).

[0045] As used herein, "heteroaryl" can refer to an aryl group containing at least one heteroatom selected from N, O, S, P and Si. Two or more heteroaryl groups are directly connected by a σ bond, or if the heteroaryl group contains two or more rings, these two or more rings can be fused together. If the heteroaryl group is a fused ring, each ring can contain one to three heteroatoms.

[0046] As used herein, unless otherwise defined, "alkenyl" refers to an aliphatic unsaturated alkenyl group of a straight-chain or branched-chain aliphatic hydrocarbon group containing at least one double bond.

[0047] As used herein, unless otherwise defined, "alkynyl" refers to an aliphatic unsaturated alkynyl group of a straight-chain or branched-chain aliphatic hydrocarbon group containing at least one triple bond.

[0048] The following describes a semiconductor photoresist composition according to some embodiments.

[0049] The semiconductor photoresist composition according to some embodiments includes a Sn-containing organometallic compound, a compound represented by Chemical Formula 1, and a solvent.

[0050] [Chemical Formula 1]

[0051]

[0052] In Chemical Formula 1,

[0053] R 1 is an unsubstituted C3 to C10 alkylene group, a substituted C1 to C10 alkylene group, a substituted or unsubstituted C4 to C20 cycloalkylene group, a substituted or unsubstituted C4 to C20 cycloalkenylene group, a substituted or unsubstituted C3 to C5 alkenylene group, a substituted or unsubstituted C3 to C5 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heterocycloalkylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof.

[0054] By including a dicarboxylic acid compound, the semiconductor photoresist composition has increased sensitivity to extreme ultraviolet light and excellent stability against line edge roughness (LER) and delay between processes.

[0055] In the examples, if R in Chemical Formula 1 1 is cyclic, when the total number of carbon atoms contained in the compound is 4 to 8, the above effects can be achieved. If R in Chemical Formula 1 1 is chain-like (e.g., a chain or a straight chain), when the total number of carbon atoms contained in the compound is 3 or more, the above effects can be achieved.

[0056] In the examples where R 1 is a straight chain, if the total number of carbon atoms contained in the compound is less than 3, the effect of improving stability is reduced. If it exceeds 10, the residue in the unexposed area after development increases and the process margin decreases.

[0057] R 1The divalent linking group can be, for example, derived from: substituted methane, substituted ethane, substituted or unsubstituted propane, substituted or unsubstituted butane, substituted or unsubstituted pentane, substituted or unsubstituted cyclopentane, substituted or unsubstituted cyclopentene, substituted or unsubstituted cyclohexane, substituted or unsubstituted tetrahydropyran, substituted or unsubstituted 1,4-dioxane, substituted or unsubstituted tetrahydrothiopyran, substituted or unsubstituted 1,4-oxathiane, substituted or unsubstituted 1,4-dithiane, substituted or unsubstituted tetrahydrothiophene, substituted or unsubstituted dihydrothiophene, substituted or unsubstituted thiophene, substituted or unsubstituted tetrahydrofuran, substituted or unsubstituted dihydrofuran, substituted or unsubstituted furan, substituted or unsubstituted oxazolidine, substituted or unsubstituted oxazole, substituted or unsubstituted oxazoline, substituted or unsubstituted pyrrolidine, substituted or unsubstituted pyrroline, substituted or unsubstituted pyrrole, substituted or unsubstituted imidazolidine, substituted or unsubstituted imidazoline, substituted or unsubstituted imidazole, substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazoline, substituted or unsubstituted pyrazolidine, substituted or unsubstituted piperidine, substituted or unsubstituted morpholine, substituted or unsubstituted piperazine, substituted or unsubstituted pyridine, substituted or unsubstituted oxazine or substituted or unsubstituted pyrazine.

[0058] As an example, the compound represented by Chemical Formula 1 can be one of the compounds listed in Group 1.

[0059] [Group 1]

[0060]

[0061]

[0062]

[0063]

[0064] For example, the compound represented by Chemical Formula 1 can be glutaric acid, pimelic acid, methylsuccinic acid, phthalic acid, cyclohexanedicarboxylic acid, furandicarboxylic acid, or a combination thereof.

[0065] Based on 100% by weight of the semiconductor photoresist composition, the compound represented by Chemical Formula 1 can be included in an amount of about 0.01 to about 10% by weight.

[0066] For example, based on 100% by weight of the semiconductor photoresist composition, the compound represented by Chemical Formula 1 can be included in an amount of about 0.01 to about 5% by weight or about 0.05 to about 5% by weight.

[0067] Based on 100% by weight of a semiconductor photoresist composition, it may include an Sn-containing organometallic compound in an amount of about 0.5% to about 30% by weight.

[0068] According to some embodiments, the semiconductor photoresist composition can improve the sensitivity of the photoresist by including an Sn-containing organometallic compound and a compound represented by Chemical Formula 1 within the above amount range.

[0069] According to some embodiments, the semiconductor photoresist composition may include an Sn-containing organometallic compound and a compound represented by Chemical Formula 1 in a weight ratio of about 99.9:0.1 to about 80:20. For example, the semiconductor photoresist composition may include an Sn-containing organometallic compound and a compound represented by Chemical Formula 1 in a weight ratio of about 95:5 to about 85:15.

[0070] If the weight ratio of the Sn-containing organometallic compound and the compound represented by Chemical Formula 1 satisfies the above range, a semiconductor photoresist composition with excellent sensitivity can be provided.

[0071] The Sn-containing organometallic compound may include at least one selected from an organic oxy group and an organic carbonyl oxy group.

[0072] The Sn-containing organometallic compound may be represented by Chemical Formula 2.

[0073] [Chemical Formula 2]

[0074]

[0075] In Chemical Formula 2,

[0076] R 2 is selected from 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, a substituted or unsubstituted C6 to C30 aralkyl group, and L a -O-R a (where L a is a substituted or unsubstituted C1 to C20 alkylene group, and R a is a substituted or unsubstituted C1 to C20 alkyl group),

[0077] R 3 to R 5Each independently 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, a substituted or unsubstituted C6-C30 aralkyl group, -OR b or -OC(=O)R c , R 3 to R 5 At least one selected from -OR b and -OC(=O)R c ,

[0078] R b 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

[0079] R c 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.

[0080] In an embodiment, the compound represented by Chemical Formula 2 includes -OR b or -OC(=O)R c as a ligand, such that a pattern formed using a semiconductor photoresist composition containing the same can exhibit excellent ultimate resolution.

[0081] In an embodiment, -OR b or -OC(=O)R c The ligand can determine the solubility of the compound represented by Chemical Formula 2 in a solvent.

[0082] R 2 can be 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,

[0083] R bmay be 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

[0084] R c may be 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.

[0085] R 2 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,

[0086] R b 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

[0087] R c may 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.

[0088] In the examples, the Sn-containing organometallic compound may be represented by Chemical Formula 3 or Chemical Formula 4.

[0089] [Chemical Formula 3]

[0090] R 6 z SnO (2-(z / 2)-(x / 2)) (OH) x

[0091] In Chemical Formula 3,

[0092] R 6 is a C1-C31 hydrocarbon group (for example, a C1-C31 hydrocarbon group), 0 < z ≤ 2, and 0 < (z + x) ≤ 4;

[0093] [Chemical Formula 4]

[0094] R7 n Sn m X l Y k

[0095] Wherein, in Chemical Formula 4,

[0096] R 7 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,

[0097] X is sulfur (S), selenium (Se), or tellurium (Te),

[0098] Y is -OR m or -OC(=O)R n ,

[0099] wherein R m 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,

[0100] R n 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

[0101] n, m, l, and k are each independently an integer from 1 to 20.

[0102] According to some embodiments, the solvent of the semiconductor photoresist composition can be an organic solvent, for example, it can be an aromatic compound (such as xylene, toluene, etc.), an alcohol (such as 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropanol, 1-propanol, etc.), an ether (such as anisole, tetrahydrofuran, etc.), an ester (such as n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, etc.), a ketone (such as methyl ethyl ketone, 2-heptanone, etc.), or a mixture thereof, but not limited thereto.

[0103] According to some embodiments, in addition to the above-mentioned Sn-containing organometallic compound, the compound represented by Chemical Formula 1, and the solvent, the semiconductor photoresist composition may further include a resin.

[0104] The resin may be a phenolic resin containing at least one aromatic group listed in Group 2.

[0105] [Group 2]

[0106]

[0107] The resin may have a weight average molecular weight of about 500 to about 20,000.

[0108] 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%.

[0109] If the resin is included within the above content range, it may have excellent etching resistance and heat resistance.

[0110] According to some embodiments, the semiconductor photoresist composition may be composed of the above Sn-containing organometallic compound, the compound represented by Chemical Formula 1, a solvent, and a resin.

[0111] 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 combinations thereof.

[0112] Surfactants may include, for example, alkylbenzenesulfonates, alkylpyridinium salts, polyethylene glycols, quaternary ammonium salts, or combinations thereof, but are not limited thereto.

[0113] Crosslinking agents may be, for example, melamine-based crosslinking agents, substituted urea-based crosslinking agents, acrylic crosslinking agents, epoxy crosslinking agents, and / or polymer-based crosslinking agents, but are not limited thereto. The crosslinking agent may be a crosslinking agent having at least two substituents for forming crosslinks. For example, compounds such as methoxymethylated biuret, butoxymethylated biuret, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, methyl methacrylate acrylate, 1,4-butanediol diglycidyl ether, glycidol, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, trimethylolpropane triglycidyl ether, 1,3-bis(glycidyloxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, and the like.

[0114] Leveling agents may be used to improve the coating flatness during the printing process and may be any suitable leveling agent commonly used in the art.

[0115] The organic acid may include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, fluorosulfonium 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.

[0116] The quencher may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0117] In some embodiments, the semiconductor photoresist composition according to the present disclosure may be mixed with an acid compound different from the compound represented by Chemical Formula 1, and the acid compound that can be mixed may include monobasic acids.

[0118] The amount of the additive used may be controlled according to the suitable or desired properties.

[0119] In an embodiment, the semiconductor photoresist composition may further include a silane coupling agent as an adhesion enhancer to improve the close contact force with the substrate (e.g., to improve the adhesion of the semiconductor photoresist composition to the substrate). The silane coupling agent may be, for example, a silane compound containing a carbon-carbon unsaturated bond, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; and / or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; trimethoxy[3-(phenylamino)propyl]silane, and / or the like, but is not limited thereto.

[0120] The semiconductor photoresist composition may form a pattern with a high aspect ratio without collapsing. 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 may 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 may be used to achieve extreme ultraviolet lithography using an EUV light source that provides light having a wavelength of about 13.5 nm.

[0121] According to some embodiments, a method of forming a pattern using the above semiconductor photoresist composition is provided. For example, the manufactured pattern may be a photoresist pattern.

[0122] A method of forming a pattern according to some embodiments includes forming an etch target layer on a substrate, coating a semiconductor photoresist composition on the etch target layer to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and etching the etch target layer using the photoresist pattern as an etch mask.

[0123] The following refers to Figures 1A - 1E a method of forming a pattern using a semiconductor photoresist composition. Figures 1A - 1E is a cross-sectional view showing a method of forming a pattern using a semiconductor photoresist composition according to some embodiments.

[0124] Referring to Figure 1A , a target to be etched is prepared. The target to be etched may be a thin film 102 formed on a semiconductor substrate 100. Hereinafter, the target to be etched is defined as the thin film 102. The surface of the thin film 102 is washed to remove impurities and / or the like remaining thereon. The thin film 102 may be, for example, a silicon nitride layer, a polysilicon layer, and / or a silicon oxide layer.

[0125] Subsequently, a bottom resist composition for forming a bottom resist 104 is spin-coated on the surface of the washed thin film 102. However, the embodiments are not limited thereto, and various known suitable coating methods may be used, such as spraying, dip coating, knife coating, printing methods such as inkjet printing and / or screen printing, and / or similar methods.

[0126] The coating process of the bottom resist may be omitted, and the process including coating the bottom resist is further described below.

[0127] Then, the coated composition is dried and baked to form a bottom resist 104 on the thin film 102. The baking may be performed at a temperature of about 100°C to about 500°C, for example, about 100°C to about 300°C.

[0128] The bottom resist 104 is formed between the substrate 100 and the photoresist layer 106, and thus unevenness of the photoresist line width and reduction of the pattern forming ability that may occur due to light scattered from the interface between the substrate 100 and the photoresist layer 106 and / or an interlayer hard mask into an unintended photoresist region can be prevented or reduced.

[0129] Referring to Figure 1B , a photoresist layer 106 is formed by coating a semiconductor photoresist composition on the bottom resist 104. The photoresist layer 106 is obtained by coating the above semiconductor photoresist composition on the thin film 102 formed on the substrate 100 and then curing by heat treatment.

[0130] In an embodiment, forming a pattern using a semiconductor photoresist composition may include coating a semiconductor resist composition on a substrate 100 having a thin film 102 by spin coating, slot coating, inkjet printing, and / or similar methods, and then drying to form a photoresist layer 106.

[0131] The semiconductor photoresist composition has been described in detail and will not be elaborated here.

[0132] Subsequently, the substrate 100 having the photoresist layer 106 is subjected to a first baking process. The first baking process may be performed at a temperature of about 80 °C to about 120 °C.

[0133] Referring to Figure 1C , the photoresist layer 106 may be selectively exposed using a patterning mask 110.

[0134] For example, the exposure may use actinic radiation including light having a high energy wavelength, such as EUV (extreme ultraviolet; wavelength of about 13.5 nm), electron beam (E-Beam), and / or similar light sources, as well 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 similar light sources.

[0135] According to some embodiments, the light used for exposure may have a wavelength in the range of about 5 nm to about 150 nm and a high energy wavelength, for example, EUV (extreme ultraviolet; wavelength 13.5 nm), electron beam (E-Beam), and / or similar light sources.

[0136] The exposed area 106b of the photoresist layer 106 has a different solubility from the unexposed area 106a of the photoresist layer 106 by forming a polymer, and the polymer is formed by a crosslinking reaction such as a condensation reaction between organometallic compounds.

[0137] Subsequently, the substrate 100 is subjected to a second baking process. The second baking process may be performed at a temperature of about 90 °C to about 200 °C. Due to the second baking process, the exposed area 106b of the photoresist layer 106 becomes insoluble in the developer.

[0138] In Figure 1D , the unexposed area 106a of the photoresist layer is dissolved and removed using a developer to form a photoresist pattern 108. Specifically, the unexposed area 106a of the photoresist layer 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.

[0139] As described above, according to some embodiments, the developer used in the method of forming a pattern can be an organic solvent. According to some embodiments, the organic solvent used in the method of forming a pattern can 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.

[0140] However, the photoresist pattern according to some embodiments is not necessarily limited to a negative image, but can be formed to have a positive image. Here, the developer for forming a positive image can be a quaternary ammonium hydroxide composition such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or a combination thereof.

[0141] As described above, exposure to light with high energy such as EUV (extreme ultraviolet; wavelength 13.5 nm), electron beam (E-Beam), and / or similar light sources, as well as light with a specific wavelength such as i-line (wavelength about 365 nm), KrF excimer laser (wavelength about 248 nm), ArF excimer laser (wavelength about 193 nm), and / or similar light sources, can provide a photoresist pattern 108 with 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.

[0142] 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, or a line width roughness of 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.

[0143] Subsequently, the resist underlayer 104 is etched using the photoresist pattern 108 as an etch mask. Through this etching process, an organic layer pattern 112 is formed. The organic layer pattern 112 can also have a width corresponding to the photoresist pattern 108.

[0144] Refer to Figure 1E , the exposed film 102 is etched by applying the photoresist pattern 108 as an etch mask. As a result, the film is formed into a film pattern 114.

[0145] The etching of the thin film 102 may be, for example, dry etching using an etching gas, and the etching gas may be, for example, CHF3, CF4, Cl2, BCl3, and / or a mixed gas thereof.

[0146] In the exposure process, the thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process using an EUV light source may have a width corresponding to that of the photoresist pattern 108. For example, the thin film pattern 114 may have a width of about 5 nm to about 100 nm, which is equal to the width of the photoresist pattern 108. For example, the thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process using an EUV light source may 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. For example, the width is less than or equal to about 20 nm, similar to the width of the photoresist pattern 108.

[0147] Hereinafter, embodiments of the present disclosure will be described in more detail through the preparation examples of the above semiconductor photoresist composition. However, the present disclosure is not technically limited by the following examples.

[0148] Synthesis of Organometallic Compounds

[0149] Synthesis Example 1

[0150] 40.7 g of tert-butyltriphenyltin and 300 g of propionic acid were added to a 250 mL two-necked round-bottom flask, and then heated under reflux for 24 hours.

[0151] The compound represented by Chemical Formula 5 was obtained by removing unreacted propionic acid under reduced pressure.

[0152] [Chemical Formula 5]

[0153]

[0154] Synthesis Example 2

[0155] 30 mL of anhydrous pentane was added to 10 g of tert-amyltin trichloride, and its temperature was maintained at 0 °C. Then, 7.4 g of diethylamine and 6.1 g of ethanol were added, and the mixture was stirred at room temperature for 1 hour. After the reaction was completed, the resulting product was filtered, concentrated, and dried under vacuum to obtain the compound represented by Chemical Formula 6.

[0156] [Chemical Formula 6]

[0157]

[0158] Synthesis Example 3

[0159] Dissolve 10 g of dibutyltin dichloride in 30 mL of diethyl ether, add 70 mL of 1 M aqueous sodium hydroxide (NaOH) solution, and then stir for 1 hour. After stirring, filter the resulting solid, wash it three times with 25 mL of deionized water, and dry it under reduced pressure at 100 °C to obtain an organometallic compound represented by Chemical Formula 7, having a weight-average molecular weight of 1,500.

[0160] [Chemical Formula 7]

[0161]

[0162] Preparation of Semiconductor Photoresist Composition

[0163] Examples 1 to 14 and Comparative Examples 1 to 4

[0164] Dissolve the organometallic compounds represented by Chemical Formulas 5 to 7 of Synthesis Examples 1 to 3 and the dicarboxylic acid compound in a mixed solution of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) mixed at a weight ratio of 7:3 at a concentration of 3 wt% respectively according to the respective weight ratios shown in Table 1, and then filter with a 0.1 µm PTFE (polytetrafluoroethylene) syringe filter to prepare a semiconductor photoresist composition.

[0165] Table 1

[0166] Organometallic compound (wt%) Dicarboxylic acid compound (wt%) Example 1 Chemical formula 5 (2.85) Glutaric acid (0.15) Example 2 Chemical formula 5 (2.85) Pimelic acid (0.15) Example 3 Chemical formula 5 (2.85) 2 - Methylsuccinic acid (0.15) Example 4 Chemical formula 5 (2.85) L - Aspartic acid (0.15) Example 5 Chemical formula 5 (2.85) Cyclohexanedicarboxylic acid (0.15) Example 6 Chemical formula 5 (2.83) Glutaric acid (0.17) Example 7 Chemical formula 5 (2.80) Glutaric acid (0.20) Example 8 Chemical formula 5 (2.75) Glutaric acid (0.25) Example 9 Chemical formula 6 (2.85) Glutaric acid (0.15) Example 10 Chemical formula 6 (2.85) Pimelic acid (0.15) Example 11 Chemical formula 6 (2.85) 2 - Methylsuccinic acid (0.15) Example 12 Chemical formula 7 (2.85) Glutaric acid (0.15) Example 13 Chemical formula 7 (2.85) Pimelic acid (0.15) Example 14 Chemical formula 7 (2.85) 2 - Methylsuccinic acid (0.15) Comparative Example 1 Chemical formula 5 (2.85) Adamantanecarboxylic acid (0.15) Comparative Example 2 Chemical formula 5 (2.85) Succinic acid (0.15) Comparative Example 3 Chemical formula 6 (2.85) Succinic acid (0.15) Comparative Example 4 Chemical formula 7 (2.85) Succinic acid (0.15)

[0167] Evaluation 1: Evaluation of Sensitivity and Line Edge Roughness (LER)

[0168] Spin-coat each of the photoresist compositions of the examples and comparative examples on a 200-mm circular silicon wafer with a surface deposited with hexamethyldisilazane (HMDS) at a speed of 1500 rpm for 30 seconds, and bake at 110 °C for 60 seconds. After coating, perform post-application bake (PAB) and leave it at room temperature (23 ± 2 °C) for 30 seconds.

[0169] Then, project a linear array of 50 circular pads with a diameter of 500 µm onto the wafer coated with the photoresist composition using extreme ultraviolet light (Lawrence Berkeley National Laboratory Microexposure Tool, MET). Here, adjust the pad exposure time to ensure that extreme ultraviolet light with an increasing dose is applied to each pad.

[0170] Then, after exposure, bake the resist and the substrate on a hot plate at 160 °C for 120 seconds. Develop the baked film with a PGMEA solvent to form a negative image. Finally, bake the obtained film on a hot plate at 150 °C for 2 minutes again to complete the process.

[0171] The residual resist thickness of the exposure pads was measured using an ellipsometer. The remaining thickness was measured for each exposure dose and plotted as a function of the exposure dose to measure the sensitivity, and the line edge roughness was measured from the FE-SEM images. The sensitivity and line edge roughness were evaluated according to the following criteria, and the results are shown in Table 2.

[0172] Sensitivity evaluation criteria

[0173] -A: Less than 16 mJ / cm²

[0174] -B: Greater than or equal to 16 mJ / cm²

[0175] Line edge roughness evaluation criteria

[0176] -○: Less than or equal to 2 nm

[0177] -△: Greater than 2 nm and less than or equal to 5 nm

[0178] -X: Greater than 5 nm

[0179] Table 2

[0180] Sensitivity Line edge roughness Example 1 A ○ Example 2 A ○ Example 3 A ○ Example 4 A ○ Example 5 A ○ Example 6 A ○ Example 7 A ○ Example 8 A ○ Example 9 A ○ Example 10 A ○ Example 11 A ○ Example 12 A ○ Example 13 A ○ Example 14 A ○ Comparative Example 1 B Ⅹ Comparative Example 2 A △ Comparative Example 3 A △ Comparative Example 4 A △

[0181] From the results in Table 2, it can be seen that the patterns formed using the semiconductor photoresist compositions of Examples 1 to 14 exhibited excellent sensitivity and LER compared to Comparative Examples 1 to 4.

[0182] Certain embodiments have been described and illustrated above. 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 transformations can be made without departing from the spirit and scope of the present disclosure. Therefore, these modified or transformed embodiments should not be understood separately from the technical idea and aspects of the present disclosure, and the modified embodiments are within the scope of the claims of the present disclosure and their equivalents.

Claims

1. A semiconductor photoresist composition, comprising: a Sn-containing organometallic compound; a compound represented by Chemical Formula 1; and a solvent: Chemical Formula 1 wherein, in Chemical Formula 1, R 1 is an unsubstituted C3-C10 alkylene group, a substituted C1-C10 alkylene group, a substituted or unsubstituted C4-C20 cycloalkylene group, a substituted or unsubstituted C4-C20 cycloalkenylene group, a substituted or unsubstituted C3-C5 alkenylene group, a substituted or unsubstituted C3-C5 alkynylene group, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C2-C30 heterocycloalkylene group, a substituted or unsubstituted C2-C30 heteroarylene group, or a combination thereof.

2. The semiconductor photoresist composition according to claim 1, wherein: R 1 is a divalent linking group derived from: substituted methane, substituted ethane, substituted or unsubstituted propane, substituted or unsubstituted butane, substituted or unsubstituted pentane, substituted or unsubstituted cyclopentane, substituted or unsubstituted cyclopentene, substituted or unsubstituted cyclohexane, substituted or unsubstituted tetrahydropyran, substituted or unsubstituted 1,4-dioxane, substituted or unsubstituted tetrahydrothiopyran, substituted or unsubstituted 1,4-oxathiane, substituted or unsubstituted 1,4-dithiane, substituted or unsubstituted tetrahydrothiophene, substituted or unsubstituted dihydrothiophene, substituted or unsubstituted thiophene, substituted or unsubstituted tetrahydrofuran, substituted or unsubstituted dihydrofuran, substituted or unsubstituted furan, substituted or unsubstituted oxazolidine, substituted or unsubstituted oxazole, substituted or unsubstituted oxazoline, substituted or unsubstituted pyrrolidine, substituted or unsubstituted pyrroline, substituted or unsubstituted pyrrole, substituted or unsubstituted imidazolidine, substituted or unsubstituted imidazoline, substituted or unsubstituted imidazole, substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazoline, substituted or unsubstituted pyrazolidine, substituted or unsubstituted piperidine, substituted or unsubstituted morpholine, substituted or unsubstituted piperazine, substituted or unsubstituted pyridine, substituted or unsubstituted oxazine or substituted or unsubstituted pyrazine.

3. The semiconductor photoresist composition according to claim 1, wherein: the compound represented by Chemical Formula 1 is one of the compounds listed in Group 1: Group 1 4. The semiconductor photoresist composition according to claim 1, wherein: the compound represented by Chemical Formula 1 is glutaric acid, pimelic acid, methylsuccinic acid, phthalic acid, cyclohexanedicarboxylic acid, furandicarboxylic acid, or a combination thereof.

5. The semiconductor photoresist composition according to claim 1, wherein: based on 100% by weight of the semiconductor photoresist composition, the compound represented by Chemical Formula 1 is included in an amount of 0.01 to 10% by weight.

6. The semiconductor photoresist composition according to claim 1, wherein: based on 100% by weight of the semiconductor photoresist composition, the compound represented by Chemical Formula 1 is included in an amount of 0.05 to 5% by weight.

7. 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.

8. The semiconductor photoresist composition according to claim 1, wherein: the Sn-containing organometallic compound and the compound represented by Chemical Formula 1 are included in a weight ratio of 99.9:0.1 to 80:

20.

9. 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.

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

11. The semiconductor photoresist composition according to claim 1, wherein: the Sn-containing organometallic compound is represented by Chemical Formula 2: Chemical Formula 2 wherein, in Chemical Formula 2, R 2 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, substituted or unsubstituted C6-C30 aralkyl, and L a -O-R a , wherein L a is a substituted or unsubstituted C1-C20 alkylene, and R a is a substituted or unsubstituted C1-C20 alkyl R 3 to R 5 each independently 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, a substituted or unsubstituted C6-C30 aralkyl group, -OR b or -OC(=O)R c , Selected from R 3 to R 5 At least one selected from -OR b and -OC(=O)R c , R b 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 R c 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.

12. The semiconductor photoresist composition according to claim 11, wherein: R 2 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 b 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 c 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.

13. The semiconductor photoresist composition according to claim 1, wherein: the Sn-containing organometallic compound is represented by Chemical Formula 3 or Chemical Formula 4: Chemical Formula 3 R 6 z SnO (2-(z / 2)-(x / 2)) (OH) x wherein, in Chemical Formula 3, R 6 is a C1 to C31 hydrocarbyl group, 0 < z ≤ 2, and 0 < (z + x) ≤ 4; Chemical Formula 4 R 7 n Sn m X l Y k wherein, in Chemical Formula 4, R 7 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 including 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 m or -OC(=O)R n , wherein R m 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 n 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 n, m, l, and k are each independently an integer from 1 to 20.

14. A method of forming a pattern, comprising: providing an etching target layer on a substrate; coating the etching target layer with the semiconductor photoresist composition according to any one of claims 1 to 13 to form a photoresist layer; patterning the photoresist layer to form a photoresist pattern; and etching the etching target layer using the photoresist pattern as an etching mask.

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