Semiconductor photoresist composition and method for forming pattern using the same

Abstract

The present invention relates to a semiconductor photoresist composition and a method for forming a pattern using the same, wherein the semiconductor photoresist composition comprises an organic metal compound and a solvent, wherein the organic metal compound comprises at least one of the compounds represented by Chemical Formula 1 to Chemical Formula 3. The details of Chemical Formula 1 to Chemical Formula 3 are as defined in the detailed description. [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3]

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2019-0127958 filed in the Korean Intellectual Property Office on October 15, 2019, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure relates to a semiconductor photoresist composition and a method of forming a pattern using the semiconductor photoresist composition. Background Art

[0004] Extreme ultraviolet (EUV) lithography has attracted attention as a basic technology for manufacturing next-generation semiconductor devices. EUV lithography is a pattern forming technology that uses EUV rays having a wavelength of about 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 about 20 nanometers) can be formed in an exposure process during the manufacture of semiconductor devices.

[0005] Extreme ultraviolet (EUV) lithography is achieved through the development of compatible photoresists, which can be performed at a spatial resolution of less than or equal to about 16 nanometers. Currently, efforts are underway to meet the insufficient specifications of conventional chemically amplified (CA) photoresists for next-generation devices, such as resolution, photospeed, and feature roughness (or also known as line edge roughness or LER).

[0006] Intrinsic image blurring due to acid-catalyzed reactions in these polymer-based photoresists limits resolution in small feature sizes, which has long been known in electron beam (e-beam) lithography. Chemically amplified (CA) photoresists are designed for high sensitivity, but may have more difficulty under EUV exposure in part because their typical elemental composition reduces the photoresist's light absorption at wavelengths of about 13.5 nanometers and thus reduces its sensitivity.

[0007] In addition, CA photoresists may have difficulty with small feature sizes due to roughness issues, and experimentally, the line edge roughness (LER) of CA photoresists increases because the photospeed is reduced in part due to the nature of the acid catalyst process. Therefore, due to these deficiencies and problems of CA photoresists, new high performance photoresists are needed in the semiconductor industry.

[0008] In order to overcome the aforementioned disadvantages of chemically amplified (CA) photosensitive compositions, inorganic photosensitive compositions have been studied. Inorganic photosensitive compositions are mainly used for negative patterning, which has resistance to removal by a developer composition due to chemical modification by a non-chemical amplification mechanism. The inorganic composition contains an inorganic element having a higher EUV absorption rate than hydrocarbons, and thus can ensure sensitivity by a non-chemical amplification mechanism, and in addition, is less sensitive to stochastic effects, and thus is known to have low line edge roughness and a smaller number of defects.

[0009] In recent years, impressive performance has been achieved when cationic hafnium metal oxide sulfate (HfSOx) materials have been used with peroxo complexing agents for 15 nm half-pitch (HP) imaging by projection EUV exposure. However, metal oxide-based inorganic resists with peroxo complexing agents are difficult to process due to the use of strong corrosive acids, poor storage stability, and difficulty in changing the structure to improve performance. Summary of the invention

[0010] One embodiment provides a semiconductor photoresist composition having improved sensitivity and storage stability.

[0011] Another embodiment provides a method of forming a pattern using a semiconductor photoresist composition.

[0012] A semiconductor photoresist composition according to an embodiment includes: an organic metal compound including at least one of the compounds represented by Chemical Formula 1 to Chemical Formula 3; and a solvent.

[0013] [Chemical formula 1]

[0014]

[0015] [Chemical formula 2]

[0016]

[0017] [Chemical formula 3]

[0018]

[0019] In Chemical Formula 1 to Chemical Formula 3,

[0020] R 1 to R 5 are independently substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof,

[0021] X 1 To X 5 Independently -ORa or -OC(=O)R b ,

[0022] R a and R b are independently hydrogen, a substituted or unsubstituted monovalent C1 to C20 saturated aliphatic hydrocarbon group, a substituted or unsubstituted monovalent C3 to C20 saturated alicyclic hydrocarbon group, a substituted or unsubstituted monovalent C2 to C20 unsaturated aliphatic hydrocarbon group containing at least one double bond or triple bond, a substituted or unsubstituted monovalent C6 to C30 aromatic hydrocarbon group, or a combination thereof, and

[0023] Y 1 To Y 5 It is independently a single bond, a substituted or unsubstituted divalent C1 to C20 saturated aliphatic hydrocarbon group, a substituted or unsubstituted divalent C3 to C20 saturated alicyclic hydrocarbon group, a substituted or unsubstituted divalent C2 to C20 unsaturated aliphatic hydrocarbon group containing at least one double bond or triple bond, a substituted or unsubstituted divalent C6 to C20 aromatic hydrocarbon group, or a combination thereof.

[0024] R 1 to R 5 may independently be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C6 to C10 aryl group, or a combination thereof,

[0025] R a and R b may independently be hydrogen, a substituted or unsubstituted monovalent C1 to C10 saturated aliphatic hydrocarbon group, a substituted or unsubstituted monovalent C3 to C10 saturated alicyclic hydrocarbon group, a substituted or unsubstituted monovalent C2 to C10 unsaturated aliphatic hydrocarbon group containing 1 or 2 double bonds or triple bonds, a substituted or unsubstituted monovalent C6 to C10 aromatic hydrocarbon group, or a combination thereof, and

[0026] Y 1 To Y 5 It may independently be a single bond, a substituted or unsubstituted divalent C1 to C8 saturated aliphatic hydrocarbon group, a substituted or unsubstituted divalent C3 to C6 saturated alicyclic hydrocarbon group, a substituted or unsubstituted divalent C2 to C8 unsaturated aliphatic hydrocarbon group containing 1 or 2 double bonds or triple bonds, a substituted or unsubstituted divalent C6 to C10 arylene group, or a combination thereof.

[0027] R 1 to R 5 may independently be methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, benzyl or a combination thereof,

[0028] R a and R bmay 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, and

[0029] Y 1 To Y 5 The groups may independently be a single bond, methylene, ethylene, propylene, butylene, cyclobutylene, cyclopentylene, cyclohexylene, vinylene, propenylene, phenylene or a combination thereof.

[0030] R 1 to R 5 may be independently one of methyl, ethyl, isopropyl, tert-butyl, phenyl and benzyl,

[0031] R a and R b may independently be methyl or ethyl, and

[0032] Y 1 To Y 5 It may independently be one of a single bond, a methylene group and an ethylene group.

[0033] In chemical formula 2, R 2 With R 3 Can be the same, and X 2 To X 5 Can be the same.

[0034] In chemical formula 3, R 4 With R 5 can be the same, and Y 4 With Y 5 Can be the same.

[0035] The semiconductor photoresist composition may include an organic metal compound including all of the compounds represented by Chemical Formula 1 to Chemical Formula 3.

[0036] The semiconductor photoresist composition may include 1 wt % to 20 wt % of at least one of the compounds represented by Chemical Formula 1 to Chemical Formula 3 based on 100 wt % of the semiconductor photoresist composition.

[0037] The semiconductor photoresist composition may include 1 wt % to 20 wt % of the compound represented by Chemical Formula 1 based on 100 wt % of the semiconductor photoresist composition.

[0038] The semiconductor photoresist composition may include 1 wt % to 20 wt % of the compound represented by Chemical Formula 2 based on 100 wt % of the semiconductor photoresist composition.

[0039] The semiconductor photoresist composition may include 1 wt % to 20 wt % of the compound represented by Chemical Formula 3 based on 100 wt % of the semiconductor photoresist composition.

[0040] The semiconductor photoresist composition may further include an additive of a surfactant, a crosslinking agent, a leveling agent, or a combination thereof.

[0041] A method for forming a pattern according to another embodiment includes: forming an etching target layer on a substrate; coating a semiconductor photoresist composition 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.

[0042] The photoresist pattern may be formed using light having a wavelength of 5 nanometers to 150 nanometers.

[0043] The semiconductor photoresist composition according to the embodiment has improved storage stability and sensitivity characteristics, and thus may provide a photoresist pattern having improved sensitivity and a high aspect ratio without pattern collapse. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figures 1 to 5 is a cross-sectional view for explaining a method of forming a pattern using a semiconductor photoresist composition according to an embodiment.

[0045] Description of Figure Numbers

[0046] 100: semiconductor substrate;

[0047] 102: thin layer;

[0048] 104: photoresist bottom layer;

[0049] 106: a photoresist layer;

[0050] 106b: exposure area;

[0051] 106a: unexposed area;

[0052] 108: photoresist pattern;

[0053] 112: organic layer pattern;

[0054] 114: Thin layer pattern. DETAILED DESCRIPTION

[0055] Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, in the description of the present disclosure, descriptions of known functions or components will be omitted in order to clarify the main points of the present disclosure.

[0056] In order to clearly describe the present disclosure, parts not related to the description are omitted, and the same reference numerals refer to the same or similar components throughout the specification. In addition, since the size and thickness of each component shown in the figure are optionally represented for convenience of description, the present disclosure is not limited to the illustrations.

[0057] In the drawings, the thickness of layers, films, panels, regions, etc. are exaggerated for clarity. In the drawings, the thickness of a portion of a layer or region, etc. is exaggerated for clarity. It should be understood that when an element such as a layer, film, region, or substrate is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present.

[0058] As used herein, "substituted" refers to the replacement of a hydrogen atom by deuterium, halogen, hydroxyl, cyano, nitro, -NRR' (wherein R and R' are independently hydrogen, a substituted or unsubstituted monovalent C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted monovalent C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted monovalent C6 to C30 aromatic hydrocarbon group), -SiRR'R" (wherein R, R' are replaced by and R" is independently hydrogen, a substituted or unsubstituted monovalent C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted monovalent C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted monovalent C6 to C30 aromatic hydrocarbon group), C1 to C30 alkyl, C1 to C10 haloalkyl, C1 to C10 alkylsilyl, C3 to C30 cycloalkyl, C6 to C30 aryl, C1 to C20 alkoxy, or a combination thereof. "Unsubstituted" means that the hydrogen atom is not replaced by another substituent and the hydrogen atom remains.

[0059] As used herein, when a specific definition is not otherwise provided, "hetero" means containing 1 to 3 heteroatoms selected from N, O, S and P and the rest carbon in one functional group.

[0060] As used herein, when no definition is otherwise provided, "alkyl" refers to a straight or branched aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" not having any double or triple bonds.

[0061] The alkyl group may be a C1 to C20 alkyl group. For example, the alkyl group may be a C1 to C10 alkyl group, a C1 to C8 alkyl group, a C1 to C6 alkyl group, or a C1 to C4 alkyl group. For example, the C1 to C4 alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.

[0062] As used herein, "saturated aliphatic hydrocarbon group" refers to a hydrocarbon group in which a bond between carbon atoms in a molecule is formed by a single bond.

[0063] The saturated aliphatic hydrocarbon group may be a C1 to C20 saturated aliphatic hydrocarbon group. For example, the saturated aliphatic hydrocarbon group may be a C1 to C10 saturated aliphatic hydrocarbon group, a C1 to C8 saturated aliphatic hydrocarbon group, a C1 to C6 saturated aliphatic hydrocarbon group, a C1 to C4 saturated aliphatic hydrocarbon group, or a C1 to C2 saturated aliphatic hydrocarbon group. For example, the C1 to C6 saturated aliphatic hydrocarbon group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a 2,2-dimethylpropyl group, or a tert-butyl group.

[0064] As used herein, a "saturated alicyclic hydrocarbon group" refers to a hydrocarbon group including a ring in which a bond between carbon and carbon atoms in the molecule is formed by a single bond.

[0065] The saturated alicyclic hydrocarbon group may be a C3 to C10 saturated alicyclic hydrocarbon group. For example, the saturated alicyclic hydrocarbon group may be a C3 to C8 saturated alicyclic hydrocarbon group, a C3 to C6 saturated alicyclic hydrocarbon group, a C3 to C5 saturated alicyclic hydrocarbon group, or a C3 or C4 saturated alicyclic hydrocarbon group. For example, the C3 to C6 saturated alicyclic hydrocarbon group may be a cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl group.

[0066] As used herein, "unsaturated aliphatic hydrocarbon group" refers to a hydrocarbon group containing bonds in which the bonds between carbon atoms in the molecule are double bonds, triple bonds, or a combination thereof.

[0067] The unsaturated aliphatic hydrocarbon group can be a C2 to C20 unsaturated aliphatic hydrocarbon group. For example, the unsaturated aliphatic hydrocarbon group can be a C2 to C10 unsaturated aliphatic hydrocarbon group, a C2 to C8 unsaturated aliphatic hydrocarbon group, a C2 to C6 unsaturated aliphatic hydrocarbon group or a C2 to C4 unsaturated aliphatic hydrocarbon group. For example, the C2 to C4 unsaturated aliphatic hydrocarbon group can be vinyl, ethynyl, allyl, 1-propenyl, 2-propenyl, 1-propynyl, 2-propynyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-butynyl, 2-butynyl and 3-butynyl.

[0068] As used herein, "unsaturated alicyclic hydrocarbon group" refers to a hydrocarbon group containing a ring containing bonds between carbon atoms that are double bonds or triple bonds.

[0069] The unsaturated alicyclic hydrocarbon group may be a C3 to C10 unsaturated alicyclic hydrocarbon group. For example, the unsaturated alicyclic hydrocarbon group may be a C3 to C8 unsaturated alicyclic hydrocarbon group, a C3 to C6 unsaturated alicyclic hydrocarbon group, a C3 to C5 unsaturated alicyclic hydrocarbon group, or a C3 or C4 unsaturated alicyclic hydrocarbon group. For example, the C3 to C6 unsaturated alicyclic hydrocarbon group may be a 1-cyclopropenyl, a 2-cyclopropenyl, a 1-cyclobutenyl, a 2-cyclobutenyl, a 1-cyclopentenyl, a 2-cyclopentenyl, a 3-cyclopentenyl, a 1-cyclohexenyl, a 2-cyclohexenyl, and a 3-cyclohexenyl.

[0070] As used herein, an "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring group in the molecule.

[0071] The aromatic hydrocarbon group may be a C6 to C10 aromatic hydrocarbon group. For example, the aromatic hydrocarbon group may be a phenyl group or a naphthyl group.

[0072] As used herein, unless otherwise defined, "alkenyl" refers to an aliphatically unsaturated alkenyl group containing at least one double bond as a straight or branched aliphatic hydrocarbon group.

[0073] As used herein, when a definition is not otherwise provided, "cycloalkyl" refers to a monovalent cyclic aliphatic hydrocarbon group.

[0074] 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 may contain monocyclic or fused-ring polycyclic functional groups (ie, rings that share adjacent pairs of carbon atoms) functional groups.

[0075] The semiconductor photoresist composition according to an embodiment of the present invention includes an organic metal compound and a solvent. The organic metal compound includes at least one of the compounds represented by Chemical Formula 1 to Chemical Formula 3.

[0076] [Chemical formula 1]

[0077]

[0078] [Chemical formula 2]

[0079]

[0080] [Chemical formula 3]

[0081]

[0082] In Chemical Formula 1 to Chemical Formula 3,

[0083] R 1 to R 5are independently substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof,

[0084] X 1 To X 5 Independently -OR a or -OC(=O)R b ,

[0085] R a and R b are independently hydrogen, a substituted or unsubstituted monovalent C1 to C20 saturated aliphatic hydrocarbon group, a substituted or unsubstituted monovalent C3 to C20 saturated alicyclic hydrocarbon group, a substituted or unsubstituted monovalent C2 to C20 unsaturated aliphatic hydrocarbon group containing at least one double bond or triple bond, a substituted or unsubstituted monovalent C6 to C30 aromatic hydrocarbon group, or a combination thereof, and

[0086] Y 1 To Y 5 It is independently a single bond, a substituted or unsubstituted divalent C1 to C20 saturated aliphatic hydrocarbon group, a substituted or unsubstituted divalent C3 to C20 saturated alicyclic hydrocarbon group, a substituted or unsubstituted divalent C2 to C20 unsaturated aliphatic hydrocarbon group containing at least one double bond or triple bond, a substituted or unsubstituted divalent C6 to C20 aromatic hydrocarbon group, or a combination thereof.

[0087] The organometallic compound may include at least one of the compounds represented by Chemical Formula 1 to Chemical Formula 3. The compounds represented by Chemical Formula 1 to Chemical Formula 3 may include tin (Sn), which strongly absorbs ultraviolet (UV) light at about 13.5 nm and thus exhibits excellent sensitivity to light having high energy.

[0088] On the other hand, the organic tin compounds represented by Chemical Formula 1 to Chemical Formula 3 include a tin (Sn) element and a dicarboxylic acid group in a molecule, and one of the dicarboxylic acid groups is bonded to the tin (Sn) element twice and exhibits a bidentate ligand form.

[0089] Since the dicarboxylic acid group is bonded to the tin (Sn) element twice and becomes a bidentate ligand, the molecule has a structure in which the dicarboxylic acid group surrounds the tin (Sn) element and thus has a much larger structure. Therefore, the dicarboxylic acid group plays a role in blocking the tin (Sn) element from contacting moisture, and thus, the semiconductor photoresist composition containing the compounds represented by Chemical Formula 1 to Chemical Formula 3 has less moisture permeation and thus has excellent storage stability.

[0090] On the other hand, in addition to the substituents R1 to R5, the compounds represented by Chemical Formulas 1 to 3 may further include an organic ligand that is hydrolyzed to form a Sn-O bond. This organic ligand is hydrolyzed under an acidic or alkaline catalyst in the presence or absence of heat treatment, and thus forms a Sn-O-Sn bond between the organic tin compounds, and thereby forms an organic tin copolymer comprising at least one of the compounds represented by Chemical Formulas 1 to 3. The organic ligand that is hydrolyzed to form a Sn-O bond may include any organic ligand known to those skilled in the art. For example, this organic ligand may include a hydroxyl group, a carboxyl group, an alkoxy group, a halogen group, a (meth)acrylate group, an epoxy group, an amino group, and the like, but is not limited thereto.

[0091] R 1 to R 5 It may independently be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C6 to C10 aryl group or a combination thereof, specifically, it may independently be one of the following: methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, benzyl or a combination thereof, and it may desirably independently be one of the following: methyl, ethyl, isopropyl, tert-butyl, phenyl and benzyl.

[0092] R 1 to R 5 It is bonded to the tin (Sn) element alone and thus forms a Sn-R bond, which provides the compound with organic solubility for the solvent. In addition, when the R functional group dissociates from the Sn-R bond during extreme ultraviolet (UV) exposure, the organic tin copolymer formed by copolymerization of at least one of the compounds represented by Chemical Formula 1 to Chemical Formula 3 generates a free radical, and the free radical forms a -Sn-O-Sn- bond through an additional free radical reaction, thereby initiating a condensation polymerization reaction between the organic tin copolymers and forming a semiconductor photoresist from the composition according to the embodiment.

[0093] R a and R bIt may independently be hydrogen, a substituted or unsubstituted monovalent C1 to C10 saturated aliphatic hydrocarbon group, a substituted or unsubstituted monovalent C3 to C10 saturated alicyclic hydrocarbon group, a substituted or unsubstituted monovalent C2 to C10 unsaturated aliphatic hydrocarbon group containing 1 or 2 double bonds or triple bonds, a substituted or unsubstituted monovalent C6 to C10 aromatic hydrocarbon group, or a combination thereof, specifically, it may independently be hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylene, benzyl, or a combination thereof, and it may desirably independently be methyl or ethyl.

[0094] Y 1 To Y 5 It may independently be a single bond, a substituted or unsubstituted divalent C1 to C8 saturated aliphatic hydrocarbon group, a substituted or unsubstituted divalent C3 to C6 saturated alicyclic hydrocarbon group, a substituted or unsubstituted divalent C2 to C8 unsaturated aliphatic hydrocarbon group containing 1 or 2 double bonds or triple bonds, a substituted or unsubstituted divalent C6 to C10 arylene group or a combination thereof, specifically, it may independently be a single bond, a methylene group, an ethylene group, a propylene group, a butylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a vinylene group, a propenylene group, a phenylene group or a combination thereof, and it may desirably independently be one of a single bond, a methylene group and an ethylene group.

[0095] Y 1 To Y 5 is a connecting group connecting two carboxyl groups in a dicarboxylic acid group, and Y 1 To Y 5 The number of carbon atoms contained in determines the length of the chain or ring of the compounds represented by Chemical Formulae 1 to 3. 1 To Y 5 The number of carbon atoms contained in is larger, and the compounds represented by Chemical Formula 1 to Chemical Formula 3 have larger molecular sizes. 1 To Y 5 When the number of carbon atoms contained in is extremely large (for example, greater than about 20), the moisture barrier effect of the dicarboxylic acid group in the molecules of the compounds represented by Chemical Formula 1 to Chemical Formula 3 may be reduced, and thus the moisture stability (that is, the storage stability characteristics of the semiconductor photoresist composition containing the compounds represented by Chemical Formula 1 to Chemical Formula 3) may be deteriorated.

[0096] R in Formula 2 2 and R 3 Can be the same, and X 2 To X 5 In other words, when R in Chemical Formula 2 2 and R 3 When the same, X 2To X 5 are the same, the compound represented by Chemical Formula 2 may have a symmetrical structure.

[0097] R in Formula 3 4 and R 5 can be the same, and Y 4 With Y 5 In other words, when R of Chemical Formula 3 4 and R 5 and Y 4 and Y 5 Meanwhile, the compound represented by Chemical Formula 3 may have a symmetrical structure.

[0098] The organometallic compound includes at least one of the compounds represented by Chemical Formula 1 to Chemical Formula 3, for example, any one compound alone or any two compounds of the compounds represented by Chemical Formula 1 to Chemical Formula 3, or all the compounds represented by Chemical Formula 1 to Chemical Formula 3.

[0099] The semiconductor photoresist composition may include at least one of the compounds represented by Chemical Formulae 1 to 3 in an amount of about 1 wt % to about 20 wt % (e.g., about 1 wt % to about 18 wt %, for example, about 1 wt % to about 15 wt %, for example, about 1 wt % to about 13 wt %, for example, about 1 wt % to about 10 wt %, for example, about 1 wt % to about 8 wt %, for example, about 1 wt % to about 5 wt %, for example, about 1 wt % to about 3 wt %) based on 100 wt % of the semiconductor photoresist composition. When the semiconductor photoresist composition includes at least one of the compounds represented by Chemical Formulae 1 to 3 within the above weight % range, moisture stability, that is, storage stability of the semiconductor photoresist composition may be improved.

[0100] The semiconductor photoresist composition may include the compound represented by Chemical Formula 1 in an amount of about 1 wt % to about 20 wt % (e.g., about 1 wt % to about 18 wt %, for example, about 1 wt % to about 15 wt %, for example, about 1 wt % to about 13 wt %, for example, about 1 wt % to about 10 wt %, for example, about 1 wt % to about 8 wt %, for example, about 1 wt % to about 5 wt %, for example, about 1 wt % to about 3 wt %), based on 100 wt % of the semiconductor photoresist composition.

[0101] The semiconductor photoresist composition may include the compound represented by Chemical Formula 2 in an amount of about 1 wt % to about 20 wt % (e.g., about 1 wt % to about 18 wt %, for example, about 1 wt % to about 15 wt %, for example, about 1 wt % to about 13 wt %, for example, about 1 wt % to about 10 wt %, for example, about 1 wt % to about 8 wt %, for example, about 1 wt % to about 5 wt %, for example, about 1 wt % to about 3 wt %), based on 100 wt % of the semiconductor photoresist composition.

[0102] The semiconductor photoresist composition may include the compound represented by Chemical Formula 3 in an amount of about 1 wt % to about 20 wt % (e.g., about 1 wt % to about 18 wt %, for example, about 1 wt % to about 15 wt %, for example, about 1 wt % to about 13 wt %, for example, about 1 wt % to about 10 wt %, for example, about 1 wt % to about 8 wt %, for example, about 1 wt % to about 5 wt %, for example, about 1 wt % to about 3 wt %), based on 100 wt % of the semiconductor photoresist composition.

[0103] The solvent included in the semiconductor photoresist composition according to the embodiment may be an organic solvent. The solvent 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, etc.), an ether (e.g., anisole, tetrahydrofuran, etc.), 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.

[0104] In an embodiment, the semiconductor photoresist composition may further include a resin in addition to the aforementioned organometallic compound and the solvent.

[0105] The resin may be a phenolic resin containing at least one or more aromatic moieties of Group 1.

[0106] [Group 1]

[0107]

[0108] The resin may have a weight average molecular weight of about 500 to about 20,000.

[0109] The resin may be included in an amount of about 0.1 wt % to about 50 wt % based on the total amount of the semiconductor photoresist composition. When the resin is included within the amount range, it may have excellent etching resistance and heat resistance.

[0110] On the other hand, the semiconductor photoresist composition according to the embodiment is desirably composed of an organic metal compound, a solvent and a resin. However, the semiconductor photoresist composition according to the above embodiment may further include an additive as needed. Examples of additives may include a surfactant, a crosslinking agent, a leveling agent or a combination thereof.

[0111] The surfactant may include, for example, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, or a combination thereof, but is not limited thereto.

[0112] The crosslinking agent may be, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent or a polymer-based crosslinking agent, but is not limited thereto. It may be a crosslinking agent having at least two crosslink-forming substituents, such as compounds such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea and the like.

[0113] The leveling agent may be used to improve the flatness of the coating during printing, and may be a known leveling agent that is commercially available.

[0114] The amount of additive used can be controlled depending on the desired properties.

[0115] In addition, the semiconductor photoresist composition may further include a silane coupling agent as an adhesion enhancer to improve the close contact force with the substrate (for example, to improve the adhesion of the semiconductor photoresist composition to the substrate). The silane coupling agent can be, for example, a silane compound containing a carbon-carbon unsaturated bond, such as vinyl trimethoxysilane, vinyl triethoxysilane, vinyl trichlorosilane, vinyl tri(β-methoxyethoxy)silane; or 3-methacryloxypropyl trimethoxysilane, 3-acryloxypropyl trimethoxysilane, p-phenylyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane; trimethoxy [3- (phenylamino) propyl] silane and the like, but is not limited thereto.

[0116] Semiconductor photoresist compositions can be formed into patterns with high aspect ratios without collapse. Therefore, in order to form fine patterns with a width of, for example, about 5 nanometers to about 100 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 70 nanometers, about 5 nanometers to about 50 nanometers, about 5 nanometers to about 40 nanometers, about 5 nanometers to about 30 nanometers, or about 5 nanometers to about 20 nanometers, semiconductor photoresist compositions can be used for photoresist processes using light with a wavelength range of about 5 nanometers to about 150 nanometers (e.g., about 5 nanometers to about 100 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 50 nanometers, about 5 nanometers to about 30 nanometers, or about 5 nanometers to about 20 nanometers). Therefore, semiconductor photoresist compositions according to embodiments can be used for realizing extreme ultraviolet (UV) lithography using an EUV light source with a wavelength of about 13.5 nanometers.

[0117] According to another embodiment, a method for forming a pattern using the semiconductor photoresist composition is provided. For example, the pattern formed can be a photoresist pattern.

[0118] The method of forming a pattern according to an embodiment includes: forming an etching target layer on a substrate; coating a semiconductor photoresist composition 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.

[0119] In the following, reference Figures 1 to 5 Methods of forming patterns using semiconductor photoresist compositions are described. Figures 1 to 5 is a cross-sectional view for explaining a method of forming a pattern using a semiconductor photoresist composition according to an embodiment.

[0120] refer to Figure 1 , an object for etching is prepared. The object for etching may be a thin layer 102 formed on a semiconductor substrate 100. Hereinafter, the object for etching is limited to the thin layer 102. The entire surface of the thin layer 102 is washed to remove impurities and the like remaining thereon. The thin layer 102 may be, for example, a silicon nitride layer, a polysilicon layer, or a silicon oxide layer.

[0121] Subsequently, a resist base layer composition for forming a photoresist base layer 104 is spin-coated on the surface of the washed thin layer 102. However, the embodiment is not limited thereto, and known various coating methods such as spray coating, dip coating, knife edge coating, printing methods (e.g., inkjet printing and screen printing), and the like may be used.

[0122] The coating process of the resist underlayer may be omitted, and hereinafter, a process including coating of the resist underlayer is described.

[0123] Next, the applied composition is dried and baked to form a photoresist bottom layer 104 on the thin layer 102. The baking may be performed at about 100°C to about 500°C (eg, about 100°C to about 300°C).

[0124] The photoresist bottom layer 104 is formed between the substrate 100 and the photoresist layer 106, and thus can prevent non-uniformity of the photoresist line width and pattern forming ability when light reflected from the interface between the substrate 100 and the photoresist layer 106 or the hard mask between the layers is scattered into unintended photoresist areas.

[0125] refer to Figure 2 , a photoresist layer 106 is formed by coating a semiconductor photoresist composition on the photoresist bottom layer 104. The photoresist layer 106 is obtained by coating the aforementioned semiconductor photoresist composition on the thin layer 102 formed on the substrate 100 and then curing the semiconductor photoresist composition by heat treatment.

[0126] More specifically, forming a pattern by using a semiconductor photoresist composition may include coating the semiconductor photoresist composition on the substrate 100 having the thin layer 102 by spin coating, slit coating, inkjet printing, and the like, and then drying the semiconductor photoresist composition to form a photoresist layer 106 .

[0127] The semiconductor photoresist composition has been shown in detail and will not be shown again.

[0128] 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.

[0129] refer to Figure 3 , the photoresist layer 106 may be selectively exposed.

[0130] For example, exposure can use activating radiation with high energy wavelengths such as EUV (extreme ultraviolet; wavelength of about 13.5 nanometers), E beam (electron beam), and the like, and short wavelength light such as i line (wavelength of about 365 nanometers), KrF excimer laser (wavelength of about 248 nanometers), ArF excimer laser (wavelength of about 193 nanometers), and the like.

[0131] More specifically, light for exposure according to an embodiment may have a short wavelength and a high energy wavelength in the range of about 5 nm to about 150 nm, such as EUV (extreme ultraviolet; wavelength of about 13.5 nm), E beam (electron beam), and the like.

[0132] By forming a polymer through a cross-linking reaction such as condensation between organic metal compounds, the exposed region 106 b of the photoresist layer 106 has a different solubility from the unexposed region 106 a of the photoresist layer 106 .

[0133] 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. The exposed region 106 b of the photoresist layer 106 becomes less soluble with respect to a developing solution due to the second baking process.

[0134] exist Figure 4 In the process, 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 using an organic solvent such as 2-heptanone and the like to complete the photoresist pattern 108 corresponding to the negative image.

[0135] As described above, the developer used in the method for forming a pattern according to the embodiment may be an organic solvent. The organic solvent used in the method for forming a pattern according to the embodiment may be, for example, ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, and the like; alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, methanol, and the like; esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, and the like; aromatic compounds such as benzene, xylene, toluene, and the like, or a combination thereof.

[0136] However, the photoresist pattern according to the embodiment is not necessarily 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.

[0137] As described above, exposure to light with high energy, such as EUV (extreme ultraviolet; wavelength of about 13.5 nanometers), E-beam (electron beam), and the like, and light with a wavelength, such as i-line (wavelength of about 365 nanometers), KrF excimer laser (wavelength of about 248 nanometers), ArF excimer laser (wavelength of about 193 nanometers), and the like, can provide a photoresist pattern 108 having a width of about 5 nanometers to about 100 nanometers in thickness. For example, the photoresist pattern 108 may have a width of about 5 nanometers to about 90 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 70 nanometers, about 5 nanometers to about 60 nanometers, about 10 nanometers to about 50 nanometers, about 10 nanometers to about 40 nanometers, about 10 nanometers to about 30 nanometers, or about 10 nanometers to about 20 nanometers in thickness.

[0138] On the other hand, the photoresist pattern 108 may have a pitch with a half pitch less than or equal to about 50 nanometers (e.g., less than or equal to about 40 nanometers, less than or equal to about 30 nanometers, or less than or equal to about 25 nanometers) and a line width roughness less than or equal to about 10 nanometers or less than or equal to about 5 nanometers.

[0139] Subsequently, the photoresist bottom layer 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.

[0140] refer to Figure 5 , the exposed thin layer 102 is etched using the photoresist pattern 108 as an etching mask. Thus, the thin layer is formed with a thin layer pattern 114.

[0141] The etching of the thin layer 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 a mixed gas thereof.

[0142] In the exposure process, the thin layer pattern 114 formed by using the photoresist pattern 108 formed through the exposure process using the EUV light source may have a width corresponding to the width of the photoresist pattern 108. For example, the thin layer pattern 114 may have a width of about 5 nanometers to about 100 nanometers, which is equal to the width of the photoresist pattern 108. For example, the thin layer pattern 114 formed by using the photoresist pattern 108 (the photoresist pattern 108 is formed by an exposure process performed using an EUV light source) may have a width of about 5 nanometers to about 90 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 70 nanometers, about 5 nanometers to about 60 nanometers, about 10 nanometers to about 50 nanometers, about 10 nanometers to about 40 nanometers, about 10 nanometers to about 30 nanometers, and about 10 nanometers to about 20 nanometers (or specifically, less than or equal to about 20 nanometers), similar to the width of the photoresist pattern 108.

[0143] Hereinafter, the present invention will be described in more detail through examples of synthesis of the aforementioned compound and preparation of the aforementioned semiconductor photoresist composition including the aforementioned compound. However, the present invention is not technically limited to the following examples.

[0144] Preparation of organometallic compounds

[0145] (Synthesis Example 1: Synthesis of a compound represented by Chemical Formula 4)

[0146] In a 50 ml 2-neck round-bottom flask, iPrSnPh3 (3 g, 7.6 mmol) and malonic acid (0.4 g, 3.8 mmol) were dissolved in 20 ml acetonitrile, and then heated and refluxed for 10 hours. Subsequently, after being completely removed by vacuum distillation, propionic acid (2 g, 27 mmol) was added thereto, and then heated and refluxed for 24 hours. Propionic acid was removed by vacuum to obtain the compound represented by Chemical Formula 4, with a yield of 80%.

[0147] [Chemical formula 4]

[0148]

[0149] (Synthesis Example 2: Synthesis of a compound represented by Chemical Formula 5)

[0150] In a 50 ml 2-neck round-bottom flask, BnSnCl (3 g, 9.5 mmol) and Et N (0.96 g, 9.5 mmol) were dissolved in 20 ml of toluene, and then, in an ice bath, malonic acid (0.5 g, 4.8 mmol) dissolved in 10 ml of acetonitrile was slowly added thereto in a dropwise manner. Subsequently, the mixture was stirred at room temperature for 3 hours, the solid produced therein was removed with a filter, and after the solvent was completely removed by vacuum distillation, Et N (1.92 g, 19 mmol) and 20 ml of toluene were added thereto. Then, propionic acid (1.4 g, 19 mmol) was slowly added thereto in a dropwise manner in an ice bath, and then stirred at room temperature for 3 hours. Then, the solid produced therein was removed with a filter, and the solvent was completely removed therein by vacuum distillation to obtain the compound represented by Chemical Formula 5, and the yield was 60%.

[0151] [Chemical formula 5]

[0152]

[0153] (Synthesis Example 3: Synthesis of a compound represented by Chemical Formula 6)

[0154] The compound represented by Chemical Formula 6 was obtained according to the same method as Synthesis Example 1, except that succinic acid was used instead of malonic acid, with a yield of 82%.

[0155] [Chemical formula 6]

[0156]

[0157] (Synthesis Example 4: Synthesis of a compound represented by Chemical Formula 7)

[0158] In a 50 ml 2-neck round-bottom flask, iPrSnPh3 (3 g, 7.6 mmol) and malonic acid (0.8 g, 7.6 mmol) were dissolved in 20 ml acetonitrile, and then heated and refluxed for 10 hours. Subsequently, after the solvent was completely removed by vacuum distillation, propionic acid (2 g, 27 mmol) was added thereto, and then heated and refluxed for 24 hours to obtain the compound represented by Chemical Formula 7, with a yield of 75%.

[0159] [Chemical formula 7]

[0160]

[0161] (Synthesis Example 5: Synthesis of a compound represented by Chemical Formula 8)

[0162] The compound represented by Chemical Formula 8 was obtained in a yield of 79% according to the same method as Synthesis Example 4, except that succinic acid was used instead of malonic acid.

[0163] [Chemical formula 8]

[0164]

[0165] (Synthesis Example 6: Synthesis of the compound represented by Chemical Formula 9)

[0166] In a 50 ml 2-necked round-bottom flask, PhSnCl (3 g, 9.9 mmol) and Et N (2 g, 19.8 mmol) were dissolved in 20 ml toluene, and in an ice bath, malonic acid (1 g, 9.9 mmol) dissolved in 10 ml acetonitrile was slowly added dropwise thereto. Subsequently, the mixture was stirred at room temperature for 3 hours, and after removing the solid produced therein with a filter, the solvent was completely removed therein by vacuum distillation, and Et was added therein again N (1 g, 9.9 mmol) and 20 ml toluene. Then, propionic acid (0.73 g, 9.9 mmol) was slowly added therein dropwise in an ice bath, and then stirred at room temperature for 3 hours. After removing the solid produced with a filter, the solvent was completely removed therein by vacuum distillation to obtain the compound represented by Chemical Formula 9, and the yield was 65%.

[0167] [Chemical formula 9]

[0168]

[0169] (Synthesis Example 7: Synthesis of a compound represented by Chemical Formula 10)

[0170] In a 50 ml 2-neck round bottom flask, iPrSnPh3 (3 g, 7.6 mmol) and malonic acid (1.2 g, 11.4 mmol) were dissolved in 20 ml acetonitrile and then heated and refluxed for 24 hours. Subsequently, the solvent was completely removed by vacuum distillation to obtain the compound represented by Chemical Formula 10 with a yield of 83%.

[0171] [Chemical formula 10]

[0172]

[0173] (Synthesis Example 8: Synthesis of a compound represented by Chemical Formula 11)

[0174] The compound represented by Chemical Formula 11 was obtained in a yield of 82% according to the same method as Synthesis Example 7, except that succinic acid was used instead of malonic acid.

[0175] [Chemical formula 11]

[0176]

[0177] (Comparative Synthesis Example 1: Synthesis of a Compound Represented by Chemical Formula 12)

[0178] Neopentyltin trichloride (10 g, 18.7 mmol) was dissolved in anhydrous pentane and then cooled to 0°C. Subsequently, diethylamine (7.4 g, 101.3 mmol) was slowly added thereto in a dropwise manner, and then ethanol (6.1 g, 101.3 mmol) was added thereto, and then stirred at room temperature for 1 hour. When the reaction was completed, the solution was filtered, concentrated, and vacuum dried to obtain the compound represented by Chemical Formula 12 with a yield of 60%.

[0179] [Chemical formula 12]

[0180]

[0181] Example 1 to Example 8

[0182] The compounds represented by Chemical Formula 4 to Chemical Formula 11 synthesized in Synthesis Examples 1 to 8 were respectively dissolved in xylene at a concentration of 2.5 wt %, and filtered with a 0.1 μm PTFE syringe filter to prepare semiconductor photoresist compositions according to Examples 1 to 8.

[0183] Example 9

[0184] The compound represented by Chemical Formula 4 synthesized in Synthesis Example 1 and the compound represented by Chemical Formula 7 synthesized in Synthesis Example 4 were mixed by the same weight and then dissolved in xylene at a concentration of 2.5 wt %, and filtered with a 0.1 μm PTFE syringe filter to prepare a semiconductor photoresist composition according to Example 9.

[0185] Example 10

[0186] The compound represented by Chemical Formula 7 synthesized in Synthesis Example 4 and the compound represented by Chemical Formula 10 synthesized in Synthesis Example 7 were mixed by the same weight and then dissolved in xylene at a concentration of 2.5 wt %, and filtered with a 0.1 μm PTFE syringe filter to prepare a semiconductor photoresist composition according to Example 10.

[0187] Example 11

[0188] The compound represented by Chemical Formula 4 synthesized in Synthesis Example 1, the compound represented by Chemical Formula 7 synthesized in Synthesis Example 4, and the compound represented by Chemical Formula 10 synthesized in Synthesis Example 7 were mixed by the same weight and then dissolved in xylene at a concentration of 2.5 wt %, and filtered with a 0.1 μm PTFE syringe filter to prepare a semiconductor photoresist composition according to Example 11.

[0189] A circular silicon wafer having a 4-inch diameter and a natural oxide surface was used as a substrate for depositing a thin film, and the substrate was pretreated under a UV ozone cleaning system for 10 minutes. Subsequently, the photoresist composition for semiconductors according to Examples 1 to 11 was spin-coated on the pretreated substrate at 1,500 rpm for 30 seconds, and baked on a hot plate at 100° C. (post-apply baked; PAB) for 120 seconds to form a thin film.

[0190] After coating and baking, the thickness of the film was measured by ellipsometry and was about 25 nanometers.

[0191] Comparative Example 1

[0192] The compound of Chemical Formula 12 in Synthesis Comparative Synthesis Example 1 was dissolved in xylene at a concentration of 2 wt %, and then filtered with a 0.1 μm PTFE syringe filter to obtain a compound according to Comparative Example 1.

[0193] Subsequently, the semiconductor photoresist composition according to Comparative Example 1 was coated on a substrate by the same process as that of Example to form a thin film.

[0194] After coating and baking, the thickness of the film was measured by ellipsometry and was approximately 20 nanometers.

[0195] (Evaluate)

[0196] Assessment 1: Assessing sensitivity

[0197] By using EUV rays (Lawrence Berkeley National Laboratory Micro Exposure Tool, Micro Exposure Tool; MET), a linear array of 50 pads having a diameter of 500 μm was irradiated into a wafer coated with each of the semiconductor photoresist compositions according to Examples 1 to 11 and Comparative Example 1. The exposure time of the pad was adjusted to apply an increased EUV dose to each pad.

[0198] Subsequently, the resist film on the wafer substrate was exposed on a hot plate at 160°C for 120 seconds and then baked (post-exposure bake; PEB). The baked films were immersed in a developer (2-heptanone) for 30 seconds, respectively, and then cleaned with the same developer for another 10 seconds to form a negative image, removing the coated area that was not exposed to EUV light. Finally, the exposure pad was baked on a hot plate at 150°C for 2 minutes to complete the process.

[0199] The residual resist thickness of the exposed pads was measured by using an ellipsometer. The residual thickness for each exposure dose was measured and plotted as a function of the exposure dose and the D depending on the type of resist. g The (Dose to gel, energy at which 95% of the initial thickness is retained) are shown in Table 1.

[0200] Assessment 2: Assessing storage stability

[0201] On the other hand, the compounds of Examples 1 to 11 and Comparative Example 1 were evaluated in terms of storage stability according to the following criteria, and the results are shown in Table 1.

[0202] [Storage stability]

[0203] The semiconductor photoresist compositions according to Examples 1 to 11 and Comparative Example 1 were allowed to stand at room temperature (0° C. to 30° C.) for a certain time and visually inspected to evaluate the degree of precipitation, and then divided into two groups depending on the following storage criteria.

[0204] -○: Can be stored for more than 1 month

[0205] X: Can be stored for less than 2 weeks

[0206] (Table 1)

[0207] Storage stability <![CDATA[D g (mJ / cm2)]]> Example 1 ○ 14.96 Example 2 ○ 10.94 Example 3 ○ 15.53 Example 4 ○ 14.96 Example 5 ○ 15.53 Example 6 ○ 20.46 Example 7 ○ 14.96 Example 8 ○ 15.53 Example 9 ○ 14.96 Example 10 ○ 14.96 Example 11 ○ 14.96 Comparative Example 1 X 25.21

[0208] Referring to Table 1, the semiconductor photoresist compositions of Examples 1 to 11 exhibited excellent storage stability compared to the semiconductor photoresist composition of Comparative Example 1, and further, the patterns formed from the semiconductor photoresist compositions of Examples 1 to 11 exhibited much better sensitivity than the pattern formed from the semiconductor photoresist composition of Comparative Example 1.

[0209] In the above, certain exemplary embodiments of the present invention have been described and illustrated, however, it is obvious to those skilled in the art that the present invention is not limited to the exemplary embodiments as described, and various modifications and conversions may be made without departing from the spirit and scope of the present invention. Therefore, the modified or converted exemplary embodiments may not be understood solely from the technical concepts and aspects of the present invention, and the modified exemplary embodiments are within the scope of the claims of the present invention.

Claims

1. A semiconductor photoresist composition comprising an organic metal compound including at least one of the compounds represented by Chemical Formula 1 to Chemical Formula 3, and a solvent, Wherein, based on 100 wt % of the semiconductor photoresist composition, the semiconductor photoresist composition includes 1 wt % to 20 wt % of at least one of the compounds represented by Chemical Formula 1 to Chemical Formula 3: [Chemical formula 1] [Chemical formula 2] [Chemical formula 3] In Chemical Formula 1 to Chemical Formula 3, R 1 to R 5 are independently substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof, X 1 To X 5 Independently -OR a or -OC(=O)R b , R a and R b are independently hydrogen, a substituted or unsubstituted monovalent C1 to C20 saturated aliphatic hydrocarbon group, a substituted or unsubstituted monovalent C3 to C20 saturated alicyclic hydrocarbon group, a substituted or unsubstituted monovalent C2 to C20 unsaturated aliphatic hydrocarbon group containing at least one double bond or triple bond, a substituted or unsubstituted monovalent C6 to C30 aromatic hydrocarbon group, or a combination thereof, and Y 1 To Y 5 It is independently a single bond, a substituted or unsubstituted divalent C1 to C20 saturated aliphatic hydrocarbon group, a substituted or unsubstituted divalent C3 to C20 saturated alicyclic hydrocarbon group, a substituted or unsubstituted divalent C2 to C20 unsaturated aliphatic hydrocarbon group containing at least one double bond or triple bond, a substituted or unsubstituted divalent C6 to C20 aromatic hydrocarbon group, or a combination thereof.

2. The semiconductor photoresist composition according to claim 1, wherein R 1 to R 5 are independently substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C6 to C10 aryl, or a combination thereof, R a and R b are independently hydrogen, a substituted or unsubstituted monovalent C1 to C10 saturated aliphatic hydrocarbon group, a substituted or unsubstituted monovalent C3 to C10 saturated alicyclic hydrocarbon group, a substituted or unsubstituted monovalent C2 to C10 unsaturated aliphatic hydrocarbon group containing 1 or 2 double bonds or triple bonds, a substituted or unsubstituted monovalent C6 to C10 aromatic hydrocarbon group, or a combination thereof, and Y 1 To Y 5 It is independently a single bond, a substituted or unsubstituted divalent C1 to C8 saturated aliphatic hydrocarbon group, a substituted or unsubstituted divalent C3 to C6 saturated alicyclic hydrocarbon group, a substituted or unsubstituted divalent C2 to C8 unsaturated aliphatic hydrocarbon group containing 1 or 2 double bonds or triple bonds, a substituted or unsubstituted divalent C6 to C10 arylene group, or a combination thereof.

3. The semiconductor photoresist composition according to claim 1, wherein R 1 to R 5 are independently methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, benzyl or a combination thereof, R a and R b are independently hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or a combination thereof, and Y 1 To Y 5 are independently a single bond, methylene, ethylene, propylene, butylene, cyclobutylene, cyclopentylene, cyclohexylene, vinylene, propenylene, phenylene or a combination thereof.

4. The semiconductor photoresist composition according to claim 1, wherein R 1 to R 5 are independently one of methyl, ethyl, isopropyl, tert-butyl, phenyl and benzyl, R a and R b are independently methyl or ethyl, Y 1 To Y 5 are independently one of a single bond, a methylene group and an ethylene group.

5. The semiconductor photoresist composition according to claim 1, wherein in Chemical Formula 2, R 2 With R 3 Same, and X 2 To X 5 are the same.

6. The semiconductor photoresist composition according to claim 1, in, In chemical formula 3, R 4 With R 5 Same, and Y 4 With Y 5 same. 7 . The semiconductor photoresist composition according to claim 1 , wherein the semiconductor photoresist composition comprises an organic metal compound, and the organic metal compound comprises all of the compounds represented by Chemical Formula 1 to Chemical Formula 3. 8 . The semiconductor photoresist composition according to claim 1 , wherein the semiconductor photoresist composition comprises 1 to 20 wt % of the compound represented by Chemical Formula 1 based on 100 wt % of the semiconductor photoresist composition. 9 . The semiconductor photoresist composition according to claim 1 , wherein the semiconductor photoresist composition comprises 1 to 20 wt % of the compound represented by Chemical Formula 2 based on 100 wt % of the semiconductor photoresist composition. 10 . The semiconductor photoresist composition according to claim 1 , wherein the semiconductor photoresist composition comprises 1 to 20 wt % of the compound represented by Chemical Formula 3 based on 100 wt % of the semiconductor photoresist composition.

11. The semiconductor photoresist composition according to claim 1, wherein the semiconductor photoresist composition further comprises an additive of a surfactant, a crosslinking agent, a leveling agent or a combination thereof.

12. A method for forming a pattern, comprising: forming an etching target layer on a substrate; applying the semiconductor photoresist composition according to any one of claims 1 to 11 on the etching target layer to form a photoresist layer; patterning the photoresist layer to form a photoresist pattern; as well as The etch target layer is etched using the photoresist pattern as an etch mask. 13 . The method of forming a pattern according to claim 12 , wherein the photoresist pattern is formed using light having a wavelength of 5 nm to 150 nm.

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