Semiconductor photoresist composition and method of forming a pattern using the same

Abstract

The present invention relates to a semiconductor photoresist composition and a method of forming a pattern using the semiconductor photoresist composition. The semiconductor photoresist composition includes a solvent and an organometallic compound represented by Chemical Formula 1. Specific details of Chemical Formula 1 are defined in the specification. The semiconductor photoresist composition can provide a photoresist pattern having excellent ultimate resolution and not collapsing even with a high aspect ratio. [Chemical Formula 1]

Description

Technical Field

[0001] The present disclosure relates to a semiconductor photoresist composition and a method of forming a pattern using the semiconductor photoresist composition. Background Art

[0002] Extreme ultraviolet (EUV) lithography has received attention as a key technology for manufacturing next-generation semiconductor devices. EUV lithography is a pattern formation technology that uses EUV rays with a wavelength of 13.5 nanometers as an exposure light source. According to EUV lithography, it is known that extremely fine patterns (e.g., less than or equal to 20 nanometers) can be formed during the exposure process in the manufacture of semiconductor devices.

[0003] EUV lithography is achieved by developing compatible photoresists that can perform with a spatial resolution of less than or equal to 16 nanometers. Currently, efforts are being made to meet the insufficient specifications of conventional chemically amplified (CA) photoresists for next-generation devices, such as resolution, photospeed, and feature roughness (or also referred to as line edge roughness or LER).

[0004] The inherent image blur due to the acid-catalyzed reaction in these polymeric photoresists limits the resolution of small feature sizes, which has long been known in electron beam (e-beam) lithography. Chemically amplified (CA) photoresists are designed for high sensitivity, but their typical elemental composition reduces the light absorption rate of the photoresist at a wavelength of 13.5 nanometers, thus reducing their sensitivity. Therefore, CA photoresists may have more difficulties in EUV exposure in part.

[0005] In addition, due to roughness problems, CA photoresists may have difficulties with small feature sizes, and experiments have shown that the line edge roughness (LER) of CA photoresists increases because the photospeed is reduced in part due to the nature of the acid-catalyzed process. Therefore, due to these defects and problems of CA photoresists, novel high-performance photoresists are needed in the semiconductor industry.

[0006] To overcome the above disadvantages of chemically amplified (CA) organic photosensitive compositions, inorganic photosensitive compositions have been studied. The inorganic photosensitive compositions are mainly used for negative patterning, which has resistance to being removed by a developer composition due to chemical modification through a non-chemically amplified mechanism. The inorganic composition contains inorganic elements with higher EUV absorptivity than hydrocarbons, so sensitivity can be ensured through a non-chemically amplified mechanism. In addition, it is less sensitive to random effects and is thus known to have low line edge roughness and few defects.

[0007] Inorganic photoresists based on peroxypolyacids of tungsten mixed with tungsten, niobium, titanium, and / or tantalum have been reported as radiation-sensitive materials for patterning (US 5061599; H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 495, 298 - 300, 1986).

[0008] These materials are effectively used for patterning large pitches in a bilayer configuration, such as far ultraviolet (UV) (deep UV), X-ray, and electron beam sources. Recently, when a cationic hafnium metal oxide sulfate (HfSOx) material is used with a peroxyzirconium complexing agent for imaging a 15-nanometer half-pitch (HP) by projection EUV exposure, impressive performance has been obtained (US2011 - 0045406; J.K. Stowers, A. Telecky, M. Kocsis, B.L. Clark, D.A. Keszler, A. Grenville, C.N. Anderson, P.P. Naulleau, Proc. SPIE, 7969, 796915, 2011). This system exhibits the highest performance of non-CA photoresists and has a practical photospeed close to the requirements of EUV photoresists. However, the hafnium metal oxide sulfate material with a peroxyzirconium complexing agent has some practical disadvantages. First, these materials are coated with a corrosive sulfuric acid / hydrogen peroxide mixture and have insufficient shelf-life stability. Second, as a composite mixture, it is not easy to change its structure to improve performance. Third, development should be carried out in a very high concentration of 25 wt% tetramethylammonium hydroxide (TMAH) solution and the like.

[0009] Recently, active research has been conducted because it is known that tin-containing molecules have excellent extreme ultraviolet absorption. Regarding the organotin polymers among them, the alkyl ligands are dissociated by light absorption or the secondary electrons generated thereby, and are crosslinked with adjacent chains through oxo bonds, so that negative patterning that may not be removable by an organic developing solution can be achieved. Such organotin polymers exhibit greatly improved sensitivity and maintain resolution and line edge roughness, but additional improvement in patterning characteristics is required for commercial availability. SUMMARY OF THE INVENTION

[0010] TECHNICAL PROBLEM

[0011] One embodiment provides a semiconductor photoresist composition having excellent resolution, solubility, and storage stability characteristics.

[0012] Another embodiment provides a method of forming a pattern using the semiconductor photoresist composition.

[0013] MEANS FOR SOLVING THE PROBLEM

[0014] The semiconductor photoresist composition according to an embodiment includes an organometallic compound represented by Chemical Formula 1 and a solvent.

[0015] [Chemical Formula 1]

[0016]

[0017] In Chemical Formula 1,

[0018] R is 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 aliphatic unsaturated organic group containing at least one double bond or triple bond, a substituted or unsubstituted C6 to C30 aryl group, an ethoxy group, a propoxy group, -C(=O)R 1 (wherein, R 1 is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group) or a combination thereof,

[0019] X, Y, and Z are each independently -OR a , -SR b , -OC(=O)R c or -SC(=O)R d ,

[0020] R a and R b are each independently 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

[0021] R c and R d each independently represents 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.

[0022] R may 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 at least one double bond or triple bond, a substituted or unsubstituted C6-C20 aryl group, ethoxy, propoxy, -C(=O)R 1 (wherein, R 1 is hydrogen or a substituted or unsubstituted C1-C8 alkyl group) or a combination thereof.

[0023] R 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, ethoxy, propoxy, formyl, acetyl, propionyl, butyryl, or a combination thereof.

[0024] R a and R b may each independently 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

[0025] R c and R d each independently represents 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.

[0026] R a and R b may each independently 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, or a combination thereof, and

[0027] R c and R dEach may independently be hydrogen, methyl, 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.

[0028] The organometallic compound may include one or a combination of compounds represented by Chemical Formula a to Chemical Formula t.

[0029] [Chemical Formula a]

[0030]

[0031] [Chemical Formula b]

[0032]

[0033] [Chemical Formula c]

[0034]

[0035] [Chemical Formula d]

[0036]

[0037] [Chemical Formula e]

[0038]

[0039] [Chemical Formula f]

[0040]

[0041] [Chemical Formula g]

[0042]

[0043] [Chemical Formula h]

[0044]

[0045] [Chemical Formula i]

[0046]

[0047] [Chemical Formula j]

[0048]

[0049] [Chemical Formula k]

[0050]

[0051] [Chemical Formula l]

[0052]

[0053] [Chemical formula m]

[0054]

[0055] [Chemical formula n]

[0056]

[0057] [Chemical formula o]

[0058]

[0059] [Chemical formula p]

[0060]

[0061] [Chemical formula q]

[0062]

[0063] [Chemical formula r]

[0064]

[0065] [Chemical formula s]

[0066]

[0067] [Chemical formula t]

[0068]

[0069] In Chemical formulas a to t, the definitions of R a to R d are the same as those described above.

[0070] Based on 100% by weight of the semiconductor photoresist composition, the semiconductor photoresist composition may contain 1% to 30% by weight of the organometallic compound represented by Chemical formula 1.

[0071] The semiconductor photoresist composition may further contain additives such as a surfactant, a crosslinking agent, a leveling agent, or a combination thereof.

[0072] The method of forming a pattern according to the embodiment 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.

[0073] The photoresist pattern may be formed using light with a wavelength of 5 nm to 150 nm.

[0074] The method of forming a pattern may further include providing an underlayer resist formed between the substrate and the photoresist layer.

[0075] The photoresist pattern may have a width of 5 nanometers to 100 nanometers.

[0076] Advantageous Effects of the Invention

[0077] Since the semiconductor photoresist composition according to the embodiment has relatively excellent resolution and is easy to process, it can provide a photoresist pattern having excellent ultimate resolution and not collapsing even with a high aspect ratio. BRIEF DESCRIPTION OF THE DRAWINGS

[0078] Figures 1 to 5 is a cross-sectional view illustrating a method of forming a pattern using a semiconductor photoresist composition according to an embodiment.

[0079] <Description of Symbols>

[0080] 100: Substrate

[0081] 102: Thin film

[0082] 104: Underlayer resist

[0083] 106: Photoresist layer

[0084] 106a: Exposed area

[0085] 106b: Unexposed area

[0086] 108: Photoresist pattern

[0087] 112: Organic layer pattern

[0088] 114: Thin film pattern DETAILED DESCRIPTION

[0089] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the following description of the present invention, well-known functions or structures will not be described for the purpose of clarifying the present invention.

[0090] To clearly illustrate the present disclosure, the description and relationships are omitted, and throughout the disclosure, the same or similar components are denoted by the same reference numerals.

[0091] In addition, since the size and thickness of each configuration shown in the drawings are arbitrarily shown for better understanding and convenience of description, the present invention is not necessarily limited thereto.

[0092] In the drawings, for clarity, the thicknesses of layers, films, panels, regions, etc. are exaggerated. In the drawings, for clarity, the thicknesses, etc. of a part of a layer or region are exaggerated. It should be understood that when an element (e.g., a layer, film, region, or substrate) is said to be “on” another element, the element can be directly on the other element or there can also be an intervening element.

[0093] As used herein, “substituted” means that a hydrogen atom is replaced by: deuterium, a halogen, a hydroxyl group, a cyano group, a nitro group, -NRR' (wherein R and R' are independently hydrogen, a substituted or unsubstituted C1 - C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 - C30 saturated or unsaturated cycloaliphatic hydrocarbon group, or a substituted or unsubstituted C6 - C30 aromatic hydrocarbon group), -SiRR'R” (wherein R, R', and R” are each independently hydrogen, a substituted or unsubstituted C1 - C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 - C30 saturated or unsaturated cycloaliphatic hydrocarbon group, or a substituted or unsubstituted C6 - C30 aromatic hydrocarbon group), a C1 - C30 alkyl group, a C1 - C10 haloalkyl group, a C1 - C10 alkylsilyl group, a C3 - C30 cycloalkyl group, a C6 - C30 aryl group, a C1 - C20 alkoxy group, or a combination thereof. “Unsubstituted” means that the hydrogen atom is not replaced by another substituent and retains the hydrogen atom.

[0094] As used herein, when no other definition is provided, “alkyl” means a straight-chain or branched-chain aliphatic hydrocarbon group. The alkyl group can be a “saturated alkyl” having no double or triple bonds.

[0095] The alkyl group can be a C1 - C8 alkyl group. For example, the alkyl group can be a C1 - C7 alkyl group, a C1 - C6 alkyl group, a C1 - C5 alkyl group, or a C1 - C4 alkyl group. For example, a C1 - C4 alkyl group can be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or 2,2-dimethylpropyl.

[0096] As used herein, when no other definition is provided, “cycloalkyl” means a monovalent cyclic aliphatic hydrocarbon group.

[0097] The cycloalkyl group can be a C3 - C8 cycloalkyl group, such as a C3 - C7 cycloalkyl group, a C3 - C6 cycloalkyl group, a C3 - C5 cycloalkyl group, or a C3 - C4 cycloalkyl group. For example, the cycloalkyl group can be cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl, but is not limited thereto.

[0098] As used herein, “aliphatic unsaturated organic group” means a hydrocarbon group including a double bond, a triple bond, or a combination thereof between carbon atoms in the molecule.

[0099] The aliphatic unsaturated organic group may be a C2-C8 aliphatic unsaturated organic group. For example, the aliphatic unsaturated organic group may be a C2-C7 aliphatic unsaturated organic group, a C2-C6 aliphatic unsaturated organic group, a C2-C5 aliphatic unsaturated organic group, or a C2-C4 aliphatic unsaturated organic group. For example, the C2-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.

[0100] As used herein, "aryl" refers to a substituent in which all atoms in the cyclic substituent have p orbitals and the p orbitals are conjugated, and may include monocyclic or fused polycyclic (i.e., rings sharing adjacent carbon atom pairs) functional groups.

[0101] As used herein, unless otherwise defined, "alkenyl" refers to an aliphatic unsaturated alkenyl group including at least one double bond, as a straight-chain or branched-chain aliphatic hydrocarbon group.

[0102] As used herein, unless otherwise defined, "alkynyl" refers to an aliphatic unsaturated alkynyl group including at least one triple bond, as a straight-chain or branched-chain aliphatic hydrocarbon group.

[0103] In the formulas described herein, S refers to the sulfur (S) element.

[0104] Hereinafter, a semiconductor photoresist composition according to an embodiment will be described.

[0105] The semiconductor photoresist composition according to an embodiment of the present invention includes an organometallic compound and a solvent, wherein the organometallic compound is represented by Chemical Formula 1.

[0106] [Chemical Formula 1]

[0107]

[0108] In Chemical Formula 1,

[0109] R 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 at least one double bond or triple bond, a substituted or unsubstituted C6-C30 aryl group, ethoxy, propoxy, -C(=O)R 1 (wherein, R 1 is hydrogen or a substituted or unsubstituted C1-C20 alkyl group) or a combination thereof,

[0110] X, Y, and Z are each independently -OR a, -SR b , -OC(=O)R c or -SC(=O)R d ,

[0111] R a and R b 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 or a combination thereof, and

[0112] 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.

[0113] The compound represented by Chemical Formula 1 is an organotin compound, in which tin can strongly absorb extreme ultraviolet (EUV) light of 13.5 nanometers, so it has excellent sensitivity to high-energy light. Therefore, compared with traditional organic and / or inorganic resists, the organotin compound according to the embodiment can exhibit excellent stability and sensitivity.

[0114] Since the organometallic compound represented by Chemical Formula 1 basically includes -SR groups, the organometallic compound forms Sn-SR bonds, and the Sn-SR bonds are stronger than Sn-OR bonds. Therefore, the organometallic compound can have high stability in water. In addition, since the Sn-SR bond has a lower bond dissociation energy for extreme ultraviolet exposure than Sn-OR, the sensitivity characteristics of the organometallic compound can be improved. Therefore, a semiconductor photoresist composition including an organometallic compound having Sn-SR bonds can be easily processed, and the storage stability, solubility characteristics and sensitivity can be improved.

[0115] On the other hand, the compound represented by Chemical Formula 1 includes X, Y and Z as ligands connected to the tin element, where X, Y and Z are each independently -OR a , -SR b , -OC(=O)R c or -SC(=O)R d . These organic ligands are hydrolyzed and dehydrated by heat treatment under an acidic, basic or neutral catalyst or hydrolyzed and dehydrated without heat treatment to form Sn-O-Sn bonds between the organotin compounds, thereby forming an organotin oxide polymer derived from the organometallic compound represented by Chemical Formula 1.

[0116] When ligands X, Y, and Z are -SR b or -SC(=O)R d the organometallic compound includes an Sn-S bond, and the bond between Sn and S has a relatively low bond strength. Since the organometallic compound of the present invention containing an Sn-S bond can have improved water stability, the storage stability and solubility of the semiconductor photoresist composition containing the same can be improved. In addition, since the bond dissociation energy for extreme ultraviolet exposure is relatively low, the Sn-S bond can exhibit excellent sensitivity. Ligands X, Y, and Z are -OR a or -OC(=O)R c and when the organometallic compound includes -OR a or -OC(=O)R c as a ligand, the pattern formed using the semiconductor photoresist composition containing the same can exhibit excellent ultimate resolution.

[0117] Therefore, when -OR a , -SR b , -OC(=O)R c or -SC(=O)R d are mixed and used as ligands of the organometallic compound, the semiconductor photoresist composition can have excellent storage stability and solubility, and at the same time also have excellent sensitivity and resolution.

[0118] In addition, X, Y, and Z of Chemical Formula 1 (i.e., -OR a , -SR b , -OC(=O)R c or -SC(=O)R d ) can determine the solubility of the compound in a solvent.

[0119] R can be, for example, 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 including at least one double bond or triple bond, a substituted or unsubstituted C6 to C20 aryl group, ethoxy, propoxy, -C(=O)R 1 (wherein, R 1 is hydrogen or a substituted or unsubstituted C1 to C8 alkyl group) or a combination thereof, such as methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, ethoxy, propoxy, formyl, acetyl, propionyl, butyryl or a combination thereof.

[0120] R a and Rb may be, for example, independently 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, such as methyl, 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.

[0121] R c and R d may each independently be, for example, 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, such as hydrogen, methyl, 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.

[0122] The organometallic compound may include one or a combination of compounds represented by Chemical Formula a to Chemical Formula t.

[0123] [Chemical Formula a]

[0124]

[0125] [Chemical Formula b]

[0126]

[0127] [Chemical Formula c]

[0128]

[0129] [Chemical Formula d]

[0130]

[0131] [Chemical Formula e]

[0132]

[0133] [Chemical Formula f]

[0134]

[0135] [Chemical Formula g]

[0136]

[0137] [Chemical formula h]

[0138]

[0139] [Chemical formula i]

[0140]

[0141] [Chemical formula j]

[0142]

[0143] [Chemical formula k]

[0144]

[0145] [Chemical formula l]

[0146]

[0147] [Chemical formula m]

[0148]

[0149] [Chemical formula n]

[0150]

[0151] [Chemical formula o]

[0152]

[0153] [Chemical formula p]

[0154]

[0155] [Chemical formula q]

[0156]

[0157] [Chemical formula r]

[0158]

[0159] [Chemical formula s]

[0160]

[0161] [Chemical formula t]

[0162]

[0163] In Chemical formulas a to Chemical formula t, for R a to R dThe definition is the same as above.

[0164] Referring to the compounds represented by Chemical Formula a to Chemical Formula t, the organometallic compound according to the embodiment may include various combinations including -OR a , -SR b , -OC(=O)R c or -SC(=O)R d as the X, Y, and Z ligands.

[0165] Conventionally used organic resists have insufficient corrosion resistance, so patterns with a high aspect ratio may collapse.

[0166] On the other hand, conventional inorganic resists (e.g., metal oxide compounds) use a mixture of sulfuric acid and hydrogen peroxide with high corrosiveness, so they are difficult to handle and have insufficient storage stability. It is relatively difficult to structurally modify them as a composite mixture to improve performance, and a developing solution with a high concentration should be used.

[0167] In contrast, the semiconductor resist composition according to the embodiment may have relatively improved corrosion resistance, sensitivity, and resolution, and can be more easily processed compared to conventional organic and / or inorganic resists because the organometallic compound includes a structural unit in which various organic groups are bonded to the central metal atom as described above.

[0168] In the semiconductor photoresist composition according to the embodiment, the organometallic compound represented by Chemical Formula 1 may be included in an amount of 1 wt% to 30 wt%, for example, 1 wt% to 25 wt%, for example, 1 wt% to 20 wt%, for example, 1 wt% to 15 wt%, for example, 1 wt% to 10 wt%, for example, 1 wt% to 5 wt% based on the total weight of the composition, but is not limited thereto. When the organometallic compound represented by Chemical Formula 1 is included in the above range, the storage stability and solubility characteristics of the composition for semiconductor photoresists are improved, which is beneficial for film formation, and the resolution characteristics are improved.

[0169] The solvent of the semiconductor resist composition according to the embodiment may be an organic solvent, and may be, for example, an aromatic compound (e.g., xylene, toluene, etc.), an alcohol (e.g., 4-methyl-2-pentenol, 4-methyl-2-propanol, 1-butanol, methanol, isopropanol, 1-propanol), an ether (e.g., anisole, tetrahydrofuran), an ester (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate), a ketone (e.g., methyl ethyl ketone, 2-heptanone), or a mixture thereof, but is not limited thereto.

[0170] In the embodiment, in addition to the organometallic compound and the solvent, the semiconductor resist composition may further include a resin.

[0171] The resin may be a phenolic resin including at least one aromatic moiety of Group 1.

[0172] [Group 1]

[0173]

[0174] The weight average molecular weight of the resin may be from 500 to 20,000.

[0175] The resin may be included in an amount of 0.1 wt% to 50 wt% based on the total amount of the semiconductor resist composition.

[0176] When the resin is included within the above content range, it may have excellent corrosion resistance and heat resistance.

[0177] On the other hand, the semiconductor resist composition according to the embodiment may be composed of an organometallic compound, a solvent, and a resin. However, the semiconductor resist composition according to the embodiment may further include additives as needed. Examples of the additives may be a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quenching agent, or a combination thereof.

[0178] The surfactant may include, for example, alkylbenzenesulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, or a combination thereof, but is not limited thereto.

[0179] The crosslinking agent may be, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, an acrylic-based crosslinking agent, an epoxy resin-based crosslinking agent, or a polymer-based crosslinking agent, but is not limited thereto. For example, it may be a crosslinking agent having at least two crosslinking-forming substituents, such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, acrylamine carbamate, acryl 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 and the like compounds.

[0180] The leveling agent may be used to improve the coating flatness during printing, and may be a commercially available known leveling agent.

[0181] The organic acid may be p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, sulfonium fluoride salt, 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.

[0182] The quenching agent can be diphenyl(p-tolyl)amine, methyl diphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0183] The amount of the additive used can be controlled according to the desired properties.

[0184] In addition, the semiconductor photoresist composition can 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 can be, for example, a silane compound including a carbon-carbon unsaturated bond, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; trimethoxy[3-(phenylamino)propyl]silane, and the like, but not limited thereto.

[0185] The semiconductor photoresist composition can be formed into a pattern with a high aspect ratio without collapse. Therefore, to form a fine pattern having a width of, for example, 5 nm to 100 nm, such as 5 nm to 80 nm, such as 5 nm to 70 nm, such as 5 nm to 50 nm, such as 5 nm to 40 nm, such as 5 nm to 30 nm, or such as 5 nm to 20 nm, the semiconductor photoresist composition can be used in a photoresist process using light with a wavelength ranging from 5 nm to 150 nm, such as 5 nm to 100 nm, 5 nm to 80 nm, 5 nm to 50 nm, 5 nm to 30 nm, or 5 nm to 20 nm. Therefore, the semiconductor photoresist composition according to the embodiment can be used to achieve extreme ultraviolet lithography using an EUV light source with a wavelength of 13.5 nm.

[0186] According to another embodiment, a method of forming a pattern using the above semiconductor photoresist composition is provided. For example, the manufactured pattern can be a photoresist pattern.

[0187] The method of forming a pattern according to the embodiment includes: forming an etching target layer on a substrate, coating the semiconductor photoresist composition on the etching target layer to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and using the photoresist pattern as an etching mask to etch the etching target layer.

[0188] Hereinafter, with reference to Figures 1 to 5 The method of forming a pattern using the semiconductor photoresist composition will be described. Figures 1 to 5A cross-sectional view illustrating a method of forming a pattern using a semiconductor photoresist composition according to an embodiment.

[0189] Refer to Figure 1 , and an object for etching is prepared. The object for etching may be a thin film 102 formed on a semiconductor substrate 100. Hereinafter, the object for etching is limited to the thin film 102. The entire surface of the thin film 102 is washed to remove impurities and the like remaining thereon. The thin film 102 may be, for example, a silicon nitride layer, a polysilicon layer, or a silicon oxide layer.

[0190] Subsequently, a resist underlayer composition for forming a resist underlayer 104 is spin-coated on the surface of the washed thin film 102. However, the embodiment is not limited thereto, and various known coating methods such as spraying, dip coating, knife coating, printing methods (such as inkjet printing and screen printing), and the like may be used.

[0191] The coating process of the resist underlayer may be omitted, and hereinafter, a process including the coating of the resist underlayer is described.

[0192] Then, the coated composition is dried and baked to form a resist underlayer 104 on the thin film 102. The baking may be performed at 100°C to 500°C, for example, 100°C to 300°C.

[0193] The resist underlayer 104 is formed between the substrate 100 and the photoresist layer 106, so that when rays reflected from the interface between the substrate 100 and the photoresist layer 106 or from the hard mask between the layers are scattered into an unintended photoresist region, non-uniformity of the photoresist line width and pattern forming ability can be prevented.

[0194] Refer to Figure 2 , and a photoresist layer 106 is formed by coating a semiconductor photoresist composition on the resist underlayer 104. The photoresist layer 106 is obtained by coating the above-described semiconductor photoresist composition on the thin film 102 formed on the substrate 100 and then curing it by heat treatment.

[0195] More specifically, forming a pattern using a semiconductor photoresist composition may include coating a semiconductor photoresist composition on the substrate 100 having the thin film 102 by spin coating, slot coating, inkjet printing, and the like, and then drying it to form a photoresist layer 106.

[0196] The semiconductor photoresist composition has been described in detail and will not be described again.

[0197] Subsequently, the substrate 100 having the photoresist layer 106 is subjected to a first baking process. The first baking process may be performed at about 80°C to about 120°C.

[0198] With reference to Figure 3 , the photoresist layer 106 can be selectively exposed.

[0199] For example, the exposure can use actinic radiation having the following light: light having a high energy wavelength, such as extreme ultraviolet light (EUV; wavelength of 13.5 nanometers), electron beam (E-Beam), and the like; and light having a short wavelength, such as i-line (wavelength of 365 nanometers), KrF excimer laser (wavelength of 248 nanometers), ArF excimer laser (wavelength of 193 nanometers), and the like.

[0200] More specifically, according to an embodiment, the light for exposure can have a short wavelength and a high energy wavelength in the range of 5 nanometers to 150 nanometers, such as extreme ultraviolet light (EUV; wavelength of 13.5 nanometers), electron beam (E-Beam), and the like.

[0201] By forming a polymer through a crosslinking reaction (such as condensation between organometallic compounds), the exposed region 106a of the photoresist layer 106 has a different solubility from the unexposed region 106b of the photoresist layer 106.

[0202] Subsequently, the substrate 100 is subjected to a second baking process. The second baking process can be performed at a temperature of 90°C to 200°C. Due to the second baking process, the exposed region 106a of the photoresist layer 106 becomes insoluble in the developing solution.

[0203] In Figure 4 , a developing solution is used to dissolve and remove the unexposed region 106b of the photoresist layer to form a photoresist pattern 108. Specifically, by using an organic solvent such as 2-heptanone and the like to dissolve and remove the unexposed region 106b of the photoresist layer, the photoresist pattern 108 corresponding to a negative image is completed.

[0204] As described above, the developing solution used in the method of forming a pattern according to an embodiment can be an organic solvent. The organic solvent used in the method of forming a pattern according to an embodiment can be, for example, a ketone, such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, and the like; an alcohol, such as 4-methyl-2-pentanol, 1-butanol, isopropyl alcohol, 1-propanol, methanol, and the like; an ester, such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, and the like; an aromatic compound, such as benzene, xylene, toluene, and the like; or a combination thereof.

[0205] However, the photoresist pattern according to the embodiment does not have to be limited to a negative image, but may be formed to have a positive image. Herein, the developer for forming the positive image may be a quaternary ammonium hydroxide composition, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or a combination thereof.

[0206] As described above, exposure to light having high energy such as extreme ultraviolet light (EUV; wavelength of 13.5 nm), electron beam (E-Beam), and the like, and light having wavelengths such as i-line (wavelength of 365 nm), KrF excimer laser (wavelength of 248 nm), ArF excimer laser (wavelength of 193 nm), etc. can provide a photoresist pattern 108 having a width of 5 nm to 100 nm. For example, the photoresist pattern 108 may have a width of 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, or 5 nm to 20 nm.

[0207] On the other hand, the photoresist pattern 108 may have a pitch with a half-pitch less than or equal to about 50 nm, such as less than or equal to about 40 nm, such as less than or equal to about 30 nm, such as less than or equal to about 20 nm, such as less than or equal to about 15 nm, and a line width roughness 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.

[0208] Subsequently, the underlying resist 104 is etched using the photoresist pattern 108 as an etching mask. Through this etching process, an organic layer pattern 112 is formed. The organic layer pattern 112 may also have a width corresponding to the width of the photoresist pattern 108.

[0209] Refer to Figure 5 , the exposed thin film 102 is etched by applying the photoresist pattern 108 as an etching mask. Thus, the thin film is formed into a thin film pattern 114.

[0210] 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, CHF 3 , CF 4 , Cl 2 , BCl 3 and their mixed gases.

[0211] In an exposure process, a thin film pattern 114 formed by using a photoresist pattern 108 may have a width corresponding to the width of the photoresist pattern 108, and the photoresist pattern 108 is formed by an exposure process using an EUV light source. For example, the thin film pattern 114 may have a width of 5 nanometers to 100 nanometers, which is equal to the width of the photoresist pattern 108. For example, like the width of the photoresist pattern 108, the thin film pattern 114 formed by using the photoresist pattern 108 may have a width of 5 nanometers to 90 nanometers, 5 nanometers to 80 nanometers, 5 nanometers to 70 nanometers, 5 nanometers to 60 nanometers, 5 nanometers to 50 nanometers, 5 nanometers to 40 nanometers, 5 nanometers to 30 nanometers, or 5 nanometers to 20 nanometers, and more specifically, a width less than or equal to 20 nanometers, and the photoresist pattern 108 is formed by an exposure process using an EUV light source.

[0212] Modes for Implementing the Present Invention

[0213] Hereinafter, the present invention will be described in more detail by way of examples of the preparation of the above semiconductor photoresist composition. However, the present invention is not technically limited by the following examples.

[0214] Examples

[0215] Synthesis Example 1: Synthesis of Intermediate A

[0216] Put Ph 4 Sn (20 g, 46.8 mmol) into a 250 mL two-neck round-bottom flask, add 60 mL of propionic acid thereto, then heat under reflux for 24 hours, and remove the unreacted propionic acid therefrom under reduced pressure, thereby obtaining a compound represented by Intermediate A with a yield of 85%.

[0217] [Intermediate A]

[0218]

[0219] Synthesis Example 2: Synthesis of Intermediate B

[0220] Put Ph 4 Sn (20 g, 46.8 mmol) into a 250 mL two-neck round-bottom flask, add 60 mL of acetic acid thereto, then heat under reflux for 24 hours, and remove the unreacted acetic acid therefrom under reduced pressure, thereby obtaining a compound represented by Intermediate B with a yield of 90%.

[0221] [Intermediate B]

[0222]

[0223] Synthesis Example 3: Synthesis of Organotin Compound

[0224] The compound represented by Intermediate A according to Synthesis Example 1 (5 g, 12.2 mmol) was placed in a 250 mL two-necked round-bottom flask, 50 mL of anhydrous toluene was added thereto, and while stirring at room temperature, a solution prepared by dissolving ethanethiol (0.8 g, 12.2 mmol) in 20 mL of anhydrous toluene was slowly added dropwise thereto over 15 minutes. Subsequently, the resulting mixture was stirred at room temperature for 24 hours. Then, the volatile solvent was removed therefrom under reduced pressure, whereby the compound represented by Chemical Formula 2 was obtained in a yield of 65%.

[0225] [Chemical Formula 2]

[0226]

[0227] Synthesis Example 4: Synthesis of Organotin Compound

[0228] Except for using dodecanethiol (2.5 g, 12.2 mmol) instead of ethanethiol, according to the same method as in Synthesis Example 3, the compound represented by Chemical Formula 3 was synthesized in a yield of 60%.

[0229] [Chemical Formula 3]

[0230]

[0231] Synthesis Example 5: Synthesis of Organotin Compound

[0232] Except for using benzenethiol (1.1 g, 12.2 mmol) instead of ethanethiol, according to the same method as in Synthesis Example 3, the compound represented by Chemical Formula 4 was synthesized in a yield of 63%.

[0233] [Chemical Formula 4]

[0234]

[0235] Synthesis Example 6: Synthesis of Organotin Compound

[0236] The compound represented by Intermediate B according to Synthesis Example 2 (5 g, 14.1 mmol) was placed in a 250 mL two-necked round-bottom flask, 50 mL of anhydrous toluene was added thereto, and while stirring at room temperature, a solution prepared by dissolving dodecanethiol (2.8 g, 14.1 mmol) in 20 mL of anhydrous toluene was slowly added dropwise thereto over 15 minutes. Then, the resulting mixture was stirred at room temperature for 24 hours. Subsequently, the volatile solvent was removed therefrom under reduced pressure, whereby the compound represented by Chemical Formula 5 was obtained in a yield of 66%.

[0237] [Chemical Formula 5]

[0238]

[0239] Synthesis Example 7: Synthesis of Organotin Compound

[0240] The compound represented by Intermediate B according to Synthesis Example 2 (5 g, 14.1 mmol) was placed in a 250 mL two-necked round-bottom flask, 50 mL of anhydrous toluene was added thereto, and while stirring at room temperature, a solution prepared by dissolving ethanethiol (5.7 g, 28.2 mmol) in 30 mL of anhydrous toluene was slowly added dropwise thereto over 15 minutes. Then, the obtained mixture was stirred at room temperature for 24 hours.

[0241] Subsequently, the volatile solvent was removed therefrom under reduced pressure, whereby the compound represented by Chemical Formula 6 was obtained in a yield of 62%.

[0242] [Chemical Formula 6]

[0243]

[0244] Comparative Synthesis Example 1

[0245] Dibutyltin dichloride (10 g, 33 mmol) was dissolved in 30 mL of diethyl ether, and 70 mL of 1 molar (M) aqueous sodium hydroxide (NaOH) solution was added thereto, followed by stirring for 1 hour. After stirring, the solid formed therein was filtered, washed three times with 25 mL of deionized water, and dried under reduced pressure at 100 °C, whereby an organometallic compound represented by Chemical Formula 7 having a weight-average molecular weight of 1,500 g / mol was obtained.

[0246] [Chemical Formula 7]

[0247]

[0248] Examples 1 to 5

[0249] Each of the compounds represented by Chemical Formulas 2 to 6 according to Synthesis Examples 3 to 7 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at a concentration of 3% by weight, and then filtered through a 0.1 μm polytetrafluoroethylene (PTFE) syringe filter, whereby the photoresist compositions according to Examples 1 to 5 were prepared.

[0250] A disc-shaped silicon wafer with a natural oxide surface and a 4-inch diameter was used as a substrate for thin film coating and was treated in an ultraviolet ozone cleaning system for 10 minutes before coating the composition. On the treated substrate, the semiconductor photoresist compositions according to Examples 1 to 5 were spin-coated at 1500 revolutions per minute (rpm) for 30 seconds, and then baked at 100 °C for 120 seconds (post-apply bake, PAB) after application to form a photoresist film.

[0251] After coating and baking, the thickness of the film was measured by ellipsometry, and the thickness was about 25 nanometers.

[0252] Comparative Example 1

[0253] A semiconductor photoresist composition according to Comparative Example 1 and a photoresist film including the same were prepared according to the same method as above, except that the compound represented by Chemical Formula 7 according to Comparative Synthesis Example 1 was dissolved in 4-methyl-2-pentanol at a concentration of 1 wt%. The film obtained after coating and baking the composition had a thickness of about 20 nanometers.

[0254] Evaluation 1: Resolution

[0255] By changing the energy and focus, the films according to Examples 1 to 5 and Comparative Example 1 formed on the disc-shaped silicon wafer in the coating method were exposed to extreme ultraviolet (EUV) light to form line / space patterns of 12 nanometers to 100 nanometers. After exposure, the films were baked at 180 °C for 120 seconds, then immersed in a petri dish containing 2-heptanone for 60 seconds and taken out, and washed with the same solvent for 10 seconds. Finally, the films were baked at 150 °C for 5 minutes, and then their pattern images were obtained by scanning electron microscopy (SEM). The highest resolution identified from the SEM images is shown in Table 1.

[0256] Evaluation 2: Sensitivity

[0257] By using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET), a linear array of 50 circular pads with a diameter of 500 microns was projected onto wafers coated with each of the photoresist compositions according to Examples 1 to 5 and Comparative Example 1. Here, the pad exposure time was adjusted to apply an increasing EUV dose to each pad.

[0258] Subsequently, the resist and the substrate were exposed on a hot plate at 160 °C for 120 seconds for post-exposure baking (PEB). The baked films were immersed in a developing solution (2-heptanone) for 30 seconds each and additionally washed with the same developer for 10 seconds, thereby forming a negative image, i.e., removing the unexposed coating areas. Finally, the films were baked on a hot plate at 150 °C for 2 minutes each, thereby completing the process.

[0259] Then, the residual resist thickness of the exposed pads was measured using an ellipsometer. The residual resist thickness for each exposure dose was measured and plotted as a function of the exposure dose, thereby showing Dg (energy level at the end of development) for each type of resist in Table 1.

[0260] Evaluation 3: Solubility and storage stability

[0261] Based on the following reference documents, the solubility and storage stability of the semiconductor photoresist compositions according to Examples 1 to 5 and Comparative Example 1 were evaluated, and the results are shown in Table 1.

[0262] [Solubility]

[0263] Based on when dissolved in propylene glycol monomethyl ether acetate by the following weights, the solubility of the compounds represented by Chemical Formulas 2 to 6 according to Synthesis Examples 3 to 7 and the compound represented by Chemical Formula 7 according to Comparative Synthesis Example 1 was evaluated at 3 levels.

[0264] ○: 3 wt% or more than 3 wt% dissolved in PGMEA

[0265] △: Less than 3 wt% dissolved in PGMEA

[0266] X: Less than 1 wt% dissolved in PGMEA

[0267] [Storage stability]

[0268] After allowing the compound to stand at 25 °C (room temperature) for a predetermined time, the degree of precipitation of the compound was visually inspected to set a storage reference, and it was evaluated according to the following 3 levels.

[0269] ○: Can be stored for 1 month or longer

[0270] △: Can be stored for at least 1 week and less than 1 month

[0271] X: Can be stored for less than 1 week

[0272] (Table 1)

[0273]

[0274] (*HP: Half pitch reference)

[0275] Referring to the results in Table 1, compared with the photoresist composition of Comparative Example 1, the semiconductor photoresist compositions according to Examples 1 to 5 exhibited excellent solubility and storage stability. In addition, compared with the pattern formed from the composition according to Comparative Example 1, the pattern formed by using the semiconductor photoresist composition exhibited excellent sensitivity. On the contrary, since the semiconductor photoresist composition according to Comparative Example 1 showed insufficient solubility in xylene solvent, it was actually difficult to evaluate the storage stability of the composition and the pattern formation using the composition.

[0276] As described above, embodiments of the present invention have been described, but the present invention is not limited to the above embodiments, and various changes and modifications can be made without departing from the gist of the present invention, which is obvious to those skilled in the art. Therefore, the modified or transformed embodiments cannot be understood separately from the technical idea and aspects of the present invention, and the modified embodiments are within the scope of the claims of the present invention.

Claims

1. A semiconductor photoresist composition comprising an organometallic compound represented by Chemical Formula 1 and a solvent, wherein based on 100% by weight of the semiconductor photoresist composition, 1% to 30% by weight of the organometallic compound represented by the Chemical Formula 1 is comprised: [Chemical Formula 1] Wherein, In the Chemical Formula 1, R 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 at least one double bond or triple bond, a substituted or unsubstituted C6-C30 aryl group, an ethoxy group, a propoxy group, -C(=O)R 1 or a combination thereof, wherein R 1 is hydrogen or a substituted or unsubstituted C1-C20 alkyl group, X, Y and Z are each independently -OR a , -SR b , -OC(=O)R c or -SC(=O)R d , R a and R b 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 or a combination thereof, and 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.

2. The semiconductor photoresist composition according to claim 1, wherein R 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 at least one double bond or triple bond, a substituted or unsubstituted C6-C20 aryl group, an ethoxy group, a propoxy group, -C(=O)R 1 or a combination thereof, wherein R 1 is hydrogen or a substituted or unsubstituted C1-C8 alkyl group.

3. The semiconductor photoresist composition according to claim 1, wherein R is methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, ethoxy, propoxy, formyl, acetyl, propionyl, butyryl, or a combination thereof.

4. The semiconductor photoresist composition according to claim 1, wherein R a and R b each independently 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 and R d each independently 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.

5. The semiconductor photoresist composition according to claim 1, wherein R a and R b each independently is methyl, 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 R c and R d each independently is hydrogen, methyl, 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.

6. The semiconductor photoresist composition according to claim 1, wherein the organometallic compound comprises one or a combination of compounds represented by Chemical Formula a to Chemical Formula t: [Chemical Formula a] [Chemical Formula b] [Chemical Formula c] [Chemical Formula d] [Chemical Formula e] [Chemical Formula f] [Chemical Formula g] [Chemical Formula h] [Chemical Formula i] [Chemical Formula j] [Chemical Formula k] [Chemical Formula l] [Chemical Formula m] [Chemical Formula n] [Chemical Formula o] [Chemical Formula p] [Chemical Formula q] [Chemical Formula r] [Chemical Formula s] [Chemical Formula t] Wherein, In the Chemical Formula a to the Chemical Formula t, R 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 at least one double bond or triple bond, a substituted or unsubstituted C6-C30 aryl group, an ethoxy group, a propoxy group, -C(=O)R 1 or a combination thereof, wherein R 1 is hydrogen or a substituted or unsubstituted C1-C20 alkyl group R a and R b 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 or a combination thereof, and 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.

7. The semiconductor photoresist composition according to claim 6, wherein R is methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, ethoxy, propoxy, formyl, acetyl, propionyl, butyryl, or a combination thereof.

8. The semiconductor photoresist composition according to claim 6, wherein R a and R b each independently is methyl, 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 R c and R d each independently is hydrogen, methyl, 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.

9. The semiconductor photoresist composition according to claim 1, further comprising an additive such as a surfactant, a crosslinking agent, a leveling agent, or a combination thereof.

10. A method of forming a pattern, comprising forming an etching target layer on a substrate, coating the semiconductor photoresist composition according to any one of claims 1 to 9 on the etching target layer 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.

11. The method of forming a pattern according to claim 10, wherein the photoresist pattern is formed using light having a wavelength of 5 nm to 150 nm.

12. The method of forming a pattern according to claim 10, further comprising providing an underlayer resist formed between the substrate and the photoresist layer.

13. The method of forming a pattern according to claim 10, wherein the photoresist pattern has a width of 5 nanometers to 100 nanometers.

Images