Semiconductor photoresist composition and method of forming pattern using the same

Abstract

Disclosed are a semiconductor photoresist composition and a method of forming a pattern using the same, the semiconductor photoresist composition comprising an organometallic compound; an acid compound containing a vinyl group; and a solvent.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2023-0095526 filed in the Korean Intellectual Property Office on July 21, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Various embodiments of the present disclosure are directed 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 technology for manufacturing next-generation semiconductor devices. EUV lithography is a pattern forming technology that uses EUV rays with a wavelength of 13.5 nm as an exposure light source. According to EUV lithography, extremely fine patterns (e.g., less than or equal to 20 nm) can be formed in the exposure process during the manufacture of semiconductor devices.

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

[0006] Intrinsic image blurring due to acid-catalyzed reactions in these polymer-based photoresists limits resolution of small feature sizes, a problem that has long existed in electron beam (e-beam) lithography. Chemically amplified (CA) photoresists are designed to achieve high sensitivity, but may have more difficulty with EUV exposure in part because their general elemental makeup reduces the absorbance of the photoresist at 13.5 nm and therefore reduces its sensitivity.

[0007] CA photoresists may have difficulty with small feature sizes due to roughness issues, and experiments have shown that the line edge roughness (LER) of CA photoresists increases because the photospeed is reduced due in part to the nature of the acid catalyst process. Therefore, due to these defects and problems of CA photoresists, it would be advantageous to use high performance photoresists in the semiconductor industry.

[0008] In order to overcome the above-mentioned disadvantages of chemically amplified (CA) organic photosensitive compositions, an inorganic photosensitive composition has been studied. The inorganic photosensitive composition is 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 with a higher EUV absorption rate than hydrocarbons, and thus can ensure sensitivity by a non-chemical amplification mechanism, and is also less sensitive to stochastic effects, and thus has low line edge roughness and a small number of defects.

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

[0010] These materials are effective for patterning large pitches of bilayer configurations using extreme ultraviolet (deep UV), X-ray, and electron beam sources. Recently, impressive performance has been achieved when cationic metal oxide hafnium sulfate (HfSOx) materials were used with peroxo complexing agents for imaging 15nm half-pitch (HP) by projection EUV exposure. This system exhibits the highest performance of non-CA photoresists and has practical photospeeds close to the levels available for EUV photoresists. However, metal oxide hafnium sulfate materials with peroxo complexing agents have some practical disadvantages. First, these materials are coated with a corrosive sulfuric acid / hydrogen peroxide mixture and have insufficient stability over shelf life. Second, as a composite mixture, it is not easy to change its structure to achieve performance improvements. Third, development should be carried out in a very high concentration of tetramethylammonium hydroxide (TMAH) solution, such as 25 wt%.

[0011] Recently, active research has been conducted considering that molecules containing tin have excellent extreme ultraviolet absorption. For organotin polymers therein, alkyl ligands are dissociated by light absorption and / or secondary electrons generated thereby, and cross-linked with adjacent chains by oxo bonds, thereby enabling negative patterning that is not removable by organic developing solutions. Such organotin polymers exhibit greatly improved sensitivity while maintaining resolution and line edge roughness, but additional improvements in patterning characteristics are required for commercial availability. Summary of the invention

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

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

[0014] A semiconductor photoresist composition according to some embodiments includes: an organometallic compound; a vinyl-containing acid compound; and a solvent.

[0015] The vinyl-containing acid compound may include one or more selected from at least one carboxyl group, at least one sulfonic acid group, and at least one phosphonic acid group.

[0016] The vinyl group-containing acid compound may be represented by any one selected from Chemical Formula 1 to Chemical Formula 3.

[0017] Chemical formula 1

[0018]

[0019] Chemical formula 2

[0020]

[0021] Chemical formula 3

[0022]

[0023] In Chemical Formula 1 to Chemical Formula 3,

[0024] R 1 to R 3 are each independently hydrogen, or a substituted or unsubstituted C1 to C10 alkyl group,

[0025] L 1 To L 3 are each independently a single bond (eg, a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, or a substituted or unsubstituted C6 to C20 arylene group, and

[0026] n1 to n3 are each independently an integer of 1 or greater.

[0027] R 1 to R 3 may each independently be hydrogen, or a substituted or unsubstituted C1 to C5 alkyl group, and

[0028] L 1 To L 3 Each may independently be a single bond (eg, a single covalent bond), a substituted or unsubstituted C1 to C5 alkylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group.

[0029] The vinyl group-containing acid compound may be one or more selected from 4-vinylbenzoic acid, vinylsulfonic acid, vinylphosphonic acid, vinylacetic acid, (meth)acrylic acid, and 1-vinylpyrazole-4-carboxylic acid.

[0030] The vinyl-containing acid compound may be included in an amount of about 0.1 wt % to about 15 wt % based on 100 wt % of the semiconductor photoresist composition.

[0031] The organometallic compound may be included in an amount of about 1 wt % to about 30 wt % based on 100 wt % of the semiconductor photoresist composition.

[0032] The organometallic compound may include tin (Sn).

[0033] The organometallic compound may include at least one selected from an organooxy group and an organocarbonyloxy group.

[0034] The organometallic compound may be represented by Chemical Formula 4.

[0035] Chemical formula 4

[0036]

[0037] In chemical formula 4,

[0038] R 4 is selected from substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C6 to C30 arylalkyl, and L a -OR a (Where L a is a substituted or unsubstituted C1 to C20 alkylene group, and R a is a substituted or unsubstituted C1 to C20 alkyl),

[0039] R 5 to R 7 Each independently selected from -OR b or -OC(=O)R c ,

[0040] R b 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 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

[0041] R cis hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof.

[0042] R 4 may be a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C4 to C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof,

[0043] R a may be a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, and

[0044] R b It may be hydrogen, substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 alkenyl, substituted or unsubstituted C2 to C8 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.

[0045] R 4 The alkyl radical may be methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, formyl, acetyl, propionyl, butyryl, valeryl, ethoxy, propoxy or a combination thereof,

[0046] R a may be ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or a combination thereof, and

[0047] R b The radical may be hydrogen, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl or a combination thereof.

[0048] The organometallic compound and the vinyl-containing acid compound may be included in a weight ratio of about 99:1 to about 80:20.

[0049] The semiconductor photoresist composition may further include additives such as, for example, a surfactant, a leveling agent, a cross-linking agent, or a combination thereof.

[0050] The method of forming a pattern according to some embodiments 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.

[0051] The photoresist pattern may be formed using light having a wavelength of about 5 nm to about 150 nm.

[0052] The method of forming a pattern may further include providing a resist bottom layer between the substrate and the photoresist layer.

[0053] The photoresist pattern may have a width of about 5 nm to about 100 nm.

[0054] The semiconductor photoresist composition according to some embodiments achieves excellent sensitivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] The drawings, together with the specification, illustrate embodiments of the presently disclosed subject matter, and, together with the description, serve to explain principles of the embodiments of the presently disclosed subject matter.

[0056] Figures 1 to 5 is a cross-sectional view for explaining a method of forming a pattern using a semiconductor photoresist composition according to some embodiments.

[0057] [Explanation of Reference Numerals]

[0058] 100: Substrate

[0059] 102: Film

[0060] 104: Resist base

[0061] 106: Photoresist layer

[0062] 106a: Exposed area

[0063] 106b: Unexposed area

[0064] 108: Photoresist pattern

[0065] 110: Patterned mask

[0066] 112: Organic layer pattern

[0067] 114: Thin film pattern DETAILED DESCRIPTION

[0068] In the following, with reference to the accompanying drawings, embodiments of the present disclosure are described in more detail. In the following description of the embodiments of the present disclosure, in order to clarify the description of the subject matter of the present disclosure, well-known functions or configurations will not be described in detail.

[0069] In order to clearly illustrate the embodiments of the present disclosure, some descriptions and / or relationships may be omitted, and throughout the present disclosure, the same or similar configuration elements may be represented by the same reference numerals. In addition, since the size and thickness of each configuration shown in the drawings may be arbitrarily shown for better understanding and ease of description, the present disclosure is not necessarily limited thereto.

[0070] In the drawings, the thickness of a layer, film, panel, region, etc. may be exaggerated for clarity. In the drawings, the thickness of a portion of a layer or region, etc. may be exaggerated for clarity. It will be understood that when an element (such as a layer, film, region, or substrate) is referred to as being "on" another element, the element may be directly on the other element or intervening elements may also be present.

[0071] The term "substituted" as used herein refers to a hydrogen atom replaced by deuterium, a halogen, a hydroxyl group, a thiol group, a cyano group, a nitro group, -NRR' (wherein R and R' are each independently hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), -SiRR'R" (wherein R, R' and R" are each independently The term "alkyl" refers to a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), a C1 to C30 alkyl group, a C1 to C10 haloalkyl group, a C1 to C10 alkylsilanyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a C1 to C20 sulfide group, or a combination thereof. "Unsubstituted" means that a hydrogen atom is not replaced by another substituent and the remaining hydrogen atoms are not replaced.

[0072] 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" without any double or triple bonds.

[0073] The alkyl group may be a C1 to C8 alkyl group. For example, the alkyl group may be a C1 to C7 alkyl group, a C1 to C6 alkyl group, or a C1 to C5 alkyl group. For example, the C1 to C5 alkyl group 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 tert-butyl group, or a 2,2-dimethylpropyl group.

[0074] As used herein, when no definition is otherwise provided, "cycloalkyl" refers to a monovalent cyclic aliphatic hydrocarbon group.

[0075] The cycloalkyl group may be a C3 to C8 cycloalkyl group, such as a C3 to C7 cycloalkyl group, a C3 to C6 cycloalkyl group, a C3 to C5 cycloalkyl group, or a C3 to C4 cycloalkyl group. For example, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, but is not limited thereto.

[0076] The "aliphatic unsaturated organic group" described herein refers to a hydrocarbon group including a double bond, a triple bond or a combination thereof in which the bonds between carbon atoms in the molecule are double bonds, triple bonds or a combination thereof.

[0077] The aliphatic unsaturated organic group may be a C2 to C8 aliphatic unsaturated organic group. For example, the aliphatic unsaturated organic group may be a C2 to C7 aliphatic unsaturated organic group, a C2 to C6 aliphatic unsaturated organic group, a C2 to C5 aliphatic unsaturated organic group, or a C2 to C4 aliphatic unsaturated organic group. For example, the C2 to C4 aliphatic unsaturated organic group may be vinyl, ethynyl, allyl, 1-propenyl, 1-methyl-1-propenyl, 2-propenyl, 2-methyl-2-propenyl, 1-propynyl, 1-methyl-1-propynyl, 2-propynyl, 2-methyl-2-propynyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-butynyl, 2-butynyl, or 3-butynyl.

[0078] The "aryl group" described herein refers to a substituent in which all atoms in a cyclic substituent have p orbitals and the p orbitals are conjugated, and may include a monocyclic or condensed-ring polycyclic (eg, rings sharing adjacent pairs of carbon atoms) functional groups.

[0079] As used herein, "heteroaryl" may refer to an aryl group comprising at least one heteroatom selected from N, O, S, P and Si. Two or more heteroaryl groups may be directly connected by a sigma bond, or when the heteroaryl group comprises two or more rings, the two or more rings may be fused together. When the heteroaryl group is a fused ring, each ring may comprise 1 to 3 heteroatoms.

[0080] As used herein, unless otherwise defined, "alkenyl" refers to an aliphatically unsaturated alkenyl group including at least one double bond, as a straight or branched aliphatic hydrocarbon group.

[0081] As used herein, unless otherwise defined, "alkynyl" refers to an aliphatically unsaturated alkynyl group including at least one triple bond, as a straight or branched aliphatic hydrocarbon group.

[0082] Hereinafter, semiconductor photoresist compositions according to some embodiments are described.

[0083] A semiconductor photoresist composition according to some embodiments may include an organometallic compound, a vinyl-containing acid compound, and a solvent.

[0084] By including the vinyl group-containing acid compound, the semiconductor photoresist composition can improve sensitivity characteristics as a polymerization reaction caused by radicals generated by EUV proceeds.

[0085] The vinyl-containing acid compound may include one or more selected from at least one carboxyl group, at least one sulfonic acid group, and at least one phosphonic acid group.

[0086] The vinyl group-containing acid compound may be represented by any one selected from Chemical Formula 1 to Chemical Formula 3.

[0087] Chemical formula 1

[0088]

[0089] Chemical formula 2

[0090]

[0091] Chemical formula 3

[0092]

[0093] In Chemical Formula 1 to Chemical Formula 3,

[0094] R 1 to R 3 are each independently hydrogen, or a substituted or unsubstituted C1 to C10 alkyl group,

[0095] L 1 To L 3 are each independently a single bond (eg, a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, or a substituted or unsubstituted C6 to C20 arylene group, and

[0096] n1 to n3 are each independently an integer of 1 or greater.

[0097] In some embodiments, when L 1 To L 3 When each of n1 to n3 is a single bond (eg, a single covalent bond), the carboxyl group, the sulfonic acid group, and the phosphonic acid group may each be mono-substituted, and in some embodiments, n1 to n3 may each be 1.

[0098] In some embodiments, when L 1 To L 3 When each is independently a substituted or unsubstituted C1 to C10 alkylene group, the carboxyl group, the sulfonic acid group, and the phosphonic acid group may each be mono-substituted or di-substituted, and in some embodiments, n1 to n3 may each be independently an integer of 1 or 2.

[0099] In some embodiments, when L1 To L 3 When each is independently a substituted or unsubstituted C6 to C20 arylene group, the carboxyl group, the sulfonic acid group, and the phosphonic acid group may each be substituted at a substitutable position in the C6 to C20 arylene group, and for example, n1 to n3 may each be independently one of integers from 1 to 10. For example, n1 to n3 may each be independently one of integers selected from 1 to 8. In some embodiments, n1 to n3 may each be independently one of integers selected from 1 to 5. For example, n1 to n3 may each be independently one of integers selected from 1 to 3.

[0100] R 1 to R 3 may be each independently hydrogen, or a substituted or unsubstituted C1 to C5 alkyl group,

[0101] L 1 To L 3 Each may independently be a single bond (eg, a single covalent bond), a substituted or unsubstituted C1 to C5 alkylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group.

[0102] The vinyl group-containing acid compound may be one or more selected from 4-vinylbenzoic acid, vinylsulfonic acid, vinylphosphonic acid, vinylacetic acid, (meth)acrylic acid, and 1-vinylpyrazole-4-carboxylic acid.

[0103] The vinyl-containing acid compound may be included in an amount of about 0.1 wt % to about 15 wt % based on 100 wt % of the semiconductor photoresist composition.

[0104] The organometallic compound may be included in an amount of about 1 wt % to about 30 wt % based on 100 wt % of the semiconductor photoresist composition.

[0105] The organometallic compound may include tin (Sn).

[0106] The organometallic compound may include at least one selected from an organooxy group and an organocarbonyloxy group.

[0107] The organometallic compound may be represented by Chemical Formula 4.

[0108] Chemical formula 4

[0109]

[0110] In chemical formula 4,

[0111] R 4is selected from substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C6 to C30 arylalkyl, and L a -OR a (Where L a is a substituted or unsubstituted C1 to C20 alkylene group, and R a is a substituted or unsubstituted C1 to C20 alkyl),

[0112] R 5 to R 7 Each independently is -OR b or -OC(=O)R c ,

[0113] R b 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 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

[0114] R c is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof.

[0115] In some embodiments, the compound represented by Chemical Formula 4 includes -OR b or -OC(=O)R c As a ligand, a pattern formed using a semiconductor photoresist composition containing the compound can exhibit excellent limiting resolution.

[0116] In some embodiments, -OR b or -OC(=O)R c The ligand may determine the solubility of the compound represented by Chemical Formula 4 in a solvent.

[0117] R 4 may be a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C4 to C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof,

[0118] R a may be a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, and

[0119] R b It may be hydrogen, substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 alkenyl, substituted or unsubstituted C2 to C8 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.

[0120] R 4 The alkyl radical may be methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, formyl, acetyl, propionyl, butyryl, valeryl, ethoxy, propoxy or a combination thereof,

[0121] R a may be ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or a combination thereof, and

[0122] R b The radical may be hydrogen, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl or a combination thereof.

[0123] The semiconductor photoresist composition according to some embodiments may include the organometallic compound and the vinyl acid compound in a weight ratio of about 99:1 to about 80:20. For example, the semiconductor photoresist composition may include the organometallic compound and the vinyl acid compound in a weight ratio of about 95:5 to about 85:15.

[0124] When the weight ratio of the organometallic compound to the vinyl-containing acid compound satisfies the above range, a semiconductor resist composition having excellent sensitivity can be provided.

[0125] The semiconductor photoresist composition according to some embodiments may improve the sensitivity of the photoresist by including the organic metal compound and the vinyl acid compound within the above content range.

[0126] The solvent of the semiconductor photoresist composition according to some embodiments may be an organic solvent, and may include, for example, aromatic compounds (e.g., xylene, toluene, etc.), alcohols (e.g., 4-methyl-2-pentenol, 4-methyl-2-propanol, 1-butanol, methanol, isopropanol, 1-propanol), ethers (e.g., anisole, tetrahydrofuran), esters (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate), ketones (e.g., methyl ethyl ketone, 2-heptanone) or mixtures thereof, but are not limited thereto.

[0127] The semiconductor photoresist composition according to some embodiments may further include a resin in addition to the above-mentioned organometallic compound, vinyl-containing acid compound, and solvent.

[0128] The resin may be a phenolic resin comprising at least one aromatic moiety from Group 2.

[0129] Group 2

[0130]

[0131] The resin may have a weight average molecular weight of about 500 to about 20,000.

[0132] 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.

[0133] When the resin is included within the above content range, the semiconductor photoresist composition may have excellent etching resistance and heat resistance.

[0134] In some embodiments, the semiconductor photoresist composition may be composed of an organometallic compound, a solvent, and a resin. However, the semiconductor photoresist composition according to some embodiments may also include additives as needed. Examples of the additives may be surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0135] The surfactant may include, for example, alkylbenzene sulfonate, alkyl pyridinium salt, polyethylene glycol, quaternary ammonium salt, or a combination thereof, but is not limited thereto.

[0136] The crosslinking agent may be, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, an acrylic crosslinking agent, an epoxy resin-based crosslinking agent, or a polymer-based crosslinking agent, but is not limited thereto. For example, the crosslinking agent 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, urethane acrylate, acryl methacrylate, 1,4-butanediol diglycidyl ether, glycidol, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, trimethylpropane triglycidyl ether, 1,3-bis(glycidyloxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, and / or methoxymethylated thiourea and / or the like.

[0137] A leveling agent may be used to improve coating flatness during printing, and may be any suitable commercially available leveling agent.

[0138] The organic acid may include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalene disulfonic acid, methanesulfonic acid, sulfonium fluoride salts, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or a combination thereof, but is not limited thereto.

[0139] The quencher can be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0140] The amount of additive used can be controlled depending on the appropriate or desired properties.

[0141] In some embodiments, the semiconductor photoresist composition may further include a silane coupling agent as an adhesion enhancer to improve the close contact force with the substrate (e.g., to improve the adhesion of the semiconductor photoresist composition to the substrate). The silane coupling agent may be, for example, a silane compound including a carbon-carbon unsaturated bond, such as, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane; and / or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-phenylyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; trimethoxy[3-(phenylamino)propyl]silane, etc., but are not limited thereto.

[0142] The semiconductor photoresist composition can be formed into a pattern with a high aspect ratio without collapse. Therefore, in order to form a fine pattern with a width of, for example, about 5nm to about 100nm, for example, about 5nm to about 80nm, for example, about 5nm to about 70nm, for example, about 5nm to about 50nm, for example, about 5nm to about 40nm, for example, about 5nm to about 30nm, or about 5nm to about 20nm, the semiconductor photoresist composition can be used for a photoresist process using a light with a wavelength between about 5nm to about 150nm, for example, about 5nm to about 100nm, about 5nm to about 80nm, about 5nm to about 50nm, about 5nm to about 30nm, or about 5nm to about 20nm. Therefore, the semiconductor photoresist composition according to some embodiments can be used to realize extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5nm.

[0143] According to some embodiments, a method for forming a pattern using the semiconductor photoresist composition is provided. For example, the pattern produced may be a photoresist pattern.

[0144] The method of forming a pattern according to some embodiments 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.

[0145] In the following, reference Figures 1 to 5 An embodiment of a method of forming a pattern using a semiconductor photoresist composition is described. Figures 1 to 5 is a cross-sectional view illustrating a method of forming a pattern using a semiconductor photoresist composition according to some embodiments.

[0146] Reference Figure 1 , an object for etching is prepared. The object for etching may be a thin film 102 located 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, and / or a silicon oxide layer.

[0147] Subsequently, a resist base layer composition for forming the resist base layer 104 is spin-coated on the surface of the washed thin film 102. However, the embodiment is not limited thereto, and various suitable coating methods such as, for example, spray coating, dip coating, knife edge coating, printing methods (such as inkjet printing and / or screen printing), and / or the like may be used.

[0148] The coating process of the resist base layer may be omitted, and hereinafter, a process including coating of the resist base layer is described.

[0149] Then, the applied composition is dried and baked to form a resist bottom layer 104 on the thin film 102. The baking may be performed at about 100°C to about 500°C, or, for example, about 100°C to about 300°C.

[0150] The resist bottom layer 104 is formed between the substrate 100 and the photoresist layer 106 (see Figure 2 ), so when the radiation reflected from the interface between the substrate 100 and the photoresist layer 106 and / or the hard mask between the layers is scattered into the unintended photoresist area, the non-uniformity of the photoresist line width and the reduction of the pattern forming ability can be prevented.

[0151] Reference Figure 2 , a photoresist layer 106 is formed by coating a semiconductor photoresist composition on the resist base layer 104. The photoresist layer 106 is obtained by coating the above-mentioned semiconductor photoresist composition on the thin film 102 located on the substrate 100 and then curing it by heat treatment.

[0152] In some embodiments, forming a pattern by using a semiconductor photoresist composition may include coating the semiconductor photoresist composition on the substrate 100 having the thin film 102 by spin coating, slit coating, inkjet printing, and / or the like coating methods, and then drying it to form a photoresist layer 106 .

[0153] The semiconductor photoresist composition has been described in detail and will not be described again in detail.

[0154] 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.

[0155] Reference Figure 3 , the photoresist layer 106 may be selectively exposed using the patterned mask 110 .

[0156] For example, exposure can use activating radiation including the following light: light with a high-energy wavelength, such as extreme ultraviolet (EUV; wavelength of about 13.5nm), electron beam (E-Beam), etc.; and light with a short wavelength, such as i-line (wavelength of about 365nm), KrF excimer laser (wavelength of about 248nm), ArF excimer laser (wavelength of about 193nm), etc.

[0157] In some embodiments, light used for exposure according to some embodiments may have a short wavelength ranging from about 5 nm to about 150 nm, as well as a high energy wavelength such as extreme ultraviolet (EUV; wavelength of 13.5 nm), electron beam (E-Beam), etc.

[0158] By forming a polymer using a cross-linking reaction (eg, a condensation reaction between organic metal compounds), the exposed region 106 a of the photoresist layer 106 has a different solubility from the unexposed region 106 b of the photoresist layer 106 .

[0159] Subsequently, the substrate 100 is subjected to a second baking process. The second baking process may be performed at a temperature of about 90° C. to about 200° C. Due to the second baking process, the exposed region 106 a of the photoresist layer 106 becomes easily insoluble in a developing solution.

[0160] exist Figure 4 In the process, a developing solution is used to dissolve and remove the unexposed area 106b of the photoresist layer to form a photoresist pattern 108. In some embodiments, an organic solvent such as, for example, 2-heptanone is used to dissolve and remove the unexposed area 106b of the photoresist layer to complete the photoresist pattern 108 corresponding to the negative image.

[0161] As described above, the developing solution used in the method for forming a pattern according to some embodiments may be an organic solvent. The organic solvent used in the method for forming a pattern according to some embodiments may be, for example, a ketone, such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, etc.; an alcohol, such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, methanol, etc.; an ester, such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, etc.; an aromatic compound, such as benzene, xylene, toluene, etc.; or a combination thereof.

[0162] However, the photoresist pattern according to some embodiments 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.

[0163] As described above, exposure to light having high energy such as extreme ultraviolet (EUV; wavelength of 13.5 nm), electron beam (E-Beam), and light having a certain wavelength such as i-line (wavelength of about 365 nm), KrF excimer laser (wavelength of about 248 nm), ArF excimer laser (wavelength of about 193 nm), etc. can provide a photoresist pattern 108 having a width of about 5 nm to about 100 nm. For example, the photoresist pattern 108 may have a width of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm.

[0164] In some embodiments, the photoresist pattern 108 may have a pitch with a half pitch less than or equal to about 50 nm, for example, less than or equal to about 40 nm, for example, less than or equal to about 30 nm, for example, less than or equal to about 20 nm, or for example, 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.

[0165] Subsequently, the resist 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.

[0166] refer to Figure 5 The exposed thin film 102 is etched by using the photoresist pattern 108 as an etching mask. Thus, the thin film is formed into a thin film pattern 114.

[0167] 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 or a mixed gas thereof.

[0168] In the exposure process, the thin film pattern 114 formed using the photoresist pattern 108 may have a width corresponding to the width of the photoresist pattern 108, which is formed by the exposure process performed using the EUV light source. For example, the thin film pattern 114 may have a width of 5 nm to 100 nm, 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 using the photoresist pattern 108 may have a width of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm, and for example has a width of less than or equal to about 20 nm, which is formed by the exposure process performed using the EUV light source.

[0169] Hereinafter, the embodiments of the present disclosure are described in more detail by preparing the above semiconductor photoresist composition. However, the present disclosure is not technically limited by the following examples.

[0170] Synthesis of organometallic compounds

[0171] Synthesis example 1

[0172] In a 250mL 2-necked round-bottom flask, 20g (51.9mmol) of Ph3SnCl was dissolved in 70ml of tetrahydrofuran (THF), and then cooled to 0°C in an ice bath. Subsequently, 1M butylmagnesium chloride (BuMgCl) THF solution (62.3mmol) was slowly added dropwise thereto. When the addition was completed, the resulting mixture was stirred at 25°C for 12 hours, thereby obtaining a compound represented by Chemical Formula 5a.

[0173] Chemical formula 5a

[0174]

[0175] The compound represented by Chemical Formula 5a (10 g, 24.6 mmol) was dissolved in 50 mL of CH2Cl2, and then 3 equivalents (73.7 mmol) of a 2M HCl diethyl ether solution were slowly added dropwise thereto at -78°C over 30 minutes. After the obtained mixture was stirred at 25°C for 12 hours, the solvent was concentrated and vacuum distilled therefrom, thereby obtaining a compound represented by Chemical Formula 5b.

[0176] Chemical formula 5b

[0177]

[0178] Subsequently, 10 g (25.6 mmol) of the compound represented by Chemical Formula 5b was slowly dropped into 25 mL of acetic acid at 25° C. and then refluxed for 12 hours. After the temperature was lowered to 25° C., the acetic acid was vacuum distilled to finally obtain the compound represented by Chemical Formula 5.

[0179] Chemical formula 5

[0180]

[0181] Synthesis example 2

[0182] The compound of Chemical Formula 5a (10 g, 24.6 mmol) was dissolved in 50 mL of CH2Cl2, and 3 equivalents (73.7 mmol) of a 2M HCl diethyl ether solution was slowly added dropwise thereto at -78°C over 30 minutes. After the obtained mixture was stirred at 25°C for 12 hours, the solvent was concentrated and vacuum distilled therefrom, thereby obtaining a compound represented by Chemical Formula 6b.

[0183] Chemical formula 6b

[0184]

[0185] Subsequently, 10 g (25.6 mmol) of the compound represented by Chemical Formula 6b was mixed with 25 mL of a mixed solution of propionic acid and methacrylic acid (volume ratio = 3:1) and then refluxed for 12 hours. After the temperature was raised to 25° C., the compound represented by Chemical Formula 6 was finally obtained by vacuum distillation.

[0186] Chemical formula 6

[0187]

[0188] Synthesis example 3

[0189] 3.7g Mg was vacuum dried in a 500mL round-bottomed flask, and I was added thereto, and 120mL THF was also added thereto in addition. Subsequently, 8.76g 1,4-bis(bromomethyl)benzene and 20g tributyltin chloride were diluted in 120mLTHF, and then slowly added to a round-bottomed flask, and then stirred. Then, NH4Cl solution and NaCl solution were used to wash the resulting product, and then dried, and then dissolved in toluene, and 4.3g (16.7mmol) SNCl was slowly added thereto at low temperatures, and then stirred for 2 hours. After removing the solvent therefrom and then using acetonitrile and pentene to extract, the acetonitrile layer was collected therefrom, the solvent was blown off therefrom, and it was added again in DCM, 1.625g triethylamine was slowly added thereto while stirring, and acetic acid was added thereto at low temperatures, and then stirred for 1 hour. Subsequently, after the obtained solid was removed using a filter, the residue was concentrated, thereby obtaining the compound represented by Chemical Formula 7.

[0190] Chemical formula 7

[0191]

[0192] Preparation of semiconductor photoresist composition

[0193] Examples 1 to 7 and Comparative Examples 1 to 5

[0194] Each of the compounds represented by Chemical Formula 5 to Chemical Formula 7 prepared by Synthesis Examples 1 to 3 and the acid compound were dissolved in propylene glycol methyl ether acetate having a concentration of 3 wt % at the weight ratio shown in Table 1, and then filtered using a 0.1 μm polytetrafluoroethylene (PTFE) syringe filter to prepare corresponding semiconductor photoresist compositions according to Examples 1 to 7 and Comparative Examples 1 to 5.

[0195] A circular silicon wafer having a diameter of 4 inches and a natural oxide surface was used as a substrate for thin film coating, and the substrate was treated in a UV ozone cleaning system for 10 minutes before the thin film was coated. On the treated substrate, each of the semiconductor photoresist compositions of Examples 1 to 7 and Comparative Examples 1 to 5 was spin-coated for 30 seconds at a speed of 1500 rpm, and then post-apply baked (PAB) was performed at 110° C. for 60 seconds to form a photoresist film.

[0196] The thickness of the film after coating and baking was measured using ellipsometry, where the thickness was approximately 25 nm.

[0197] Assessment 1: Sensitivity Assessment

[0198] A linear array consisting of 50 circular pads each having a diameter of 500 μm was projected onto a wafer coated with each of the photoresist compositions of Examples 1 to 7 and Comparative Examples 1 and 5 using EUV light (Micro Exposure Tool, MET, Lawrence Berkeley National Laboratory). The EUV dose was gradually increased and applied to each pad by adjusting the pad exposure time.

[0199] Subsequently, the resist and substrate were exposed on a hot plate at 160°C for 120 seconds, and then post-exposure baked (PEB) was performed. The baked film was immersed in a developer (2-heptanone) for 30 seconds and washed with the same developer for another 10 seconds to form a negative image, i.e., to remove the unexposed coating area. Finally, the exposed pad was baked on a hot plate at 150°C for 2 minutes, thereby completing the process.

[0200] The residual resist thickness of the exposed pad was measured using an ellipsometer. The residual thickness at each exposure dose was measured and plotted as a function of the exposure dose, thereby evaluating the Dg (energy level at which development is completed) of each resist according to the following criteria, and the results are shown in Table 1.

[0201] ※Evaluation standard (Dg value)

[0202] A: less than 16mJ / cm 2

[0203] B: greater than or equal to 16mJ / cm 2

[0204] Table 1

[0205]

[0206] Referring to the results of Table 1, the patterns formed using the semiconductor photoresist compositions according to Examples 1 to 7 showed excellent sensitivity compared to the patterns formed using the semiconductor photoresist compositions according to Comparative Examples 1 to 5.

[0207] In the above, exemplary embodiments of the present disclosure have been described and illustrated, however, it should be obvious to those skilled in the art that the present disclosure is not limited to the described embodiments, and various modifications and changes may be made without departing from the spirit and scope of the present disclosure. Therefore, the modified or changed embodiments themselves may not be understood separately from the technical ideas and aspects of the present disclosure, and the modified embodiments are within the scope of the appended claims of the present disclosure and their equivalents.

Claims

1. A semiconductor photoresist composition comprising: Organometallic compounds; A vinyl-containing acid compound; and Solvent.

2. The semiconductor photoresist composition according to claim 1, wherein: The vinyl-containing acid compound includes one or more selected from at least one carboxyl group, at least one sulfonic acid group, and at least one phosphonic acid group.

3. The semiconductor photoresist composition according to claim 1, wherein: The vinyl-containing acid compound is represented by any one selected from Chemical Formula 1 to Chemical Formula 3, Chemical formula 1 Chemical formula 2 Chemical formula 3 Among them, in Chemical Formula 1 to Chemical Formula 3, R 1 to R 3 are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group, L 1 To L 3 are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a substituted or unsubstituted C6 to C20 arylene group, and n1 to n3 are each independently an integer of 1 or greater.

4. The semiconductor photoresist composition according to claim 3, wherein: R 1 to R 3 are each independently hydrogen or a substituted or unsubstituted C1 to C5 alkyl group, and L 1 To L 3 Each is independently a single bond, a substituted or unsubstituted C1 to C5 alkylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group.

5. The semiconductor photoresist composition according to claim 1, wherein: The vinyl group-containing acid compound includes one or more selected from 4-vinylbenzoic acid, vinylsulfonic acid, vinylphosphonic acid, vinylacetic acid, (meth)acrylic acid, and 1-vinylpyrazole-4-carboxylic acid.

6. The semiconductor photoresist composition according to claim 1, wherein: The vinyl group-containing acid compound is included in an amount of 0.1 wt % to 15 wt % based on 100 wt % of the semiconductor photoresist composition.

7. The semiconductor photoresist composition according to claim 1, wherein: The organometallic compound is included in an amount of 1 wt % to 30 wt % based on 100 wt % of the semiconductor photoresist composition.

8. The semiconductor photoresist composition according to claim 1, wherein: The organometallic compound includes tin.

9. The semiconductor photoresist composition according to claim 1, wherein: The organometallic compound includes at least one selected from an organooxy group and an organocarbonyloxy group.

10. The semiconductor photoresist composition according to claim 1, wherein: The organometallic compound is represented by Chemical Formula 4: Chemical formula 4 Among them, in chemical formula 4, R 4 is selected from substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C6 to C30 arylalkyl, and L a -OR a , where L a is a substituted or unsubstituted C1 to C20 alkylene group, and R a is a substituted or unsubstituted C1 to C20 alkyl group, R 5 to R 7 Each independently is -OR b or -OC(=O)R c , R b 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 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 R c is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof.

11. The semiconductor photoresist composition according to claim 10, wherein: R 4 is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C4 to C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof, R a is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, and R b is hydrogen, substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 alkenyl, substituted or unsubstituted C2 to C8 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.

12. The semiconductor photoresist composition according to claim 10, wherein: R 4 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, formyl, acetyl, propionyl, butyryl, valeryl, ethoxy, propoxy or a combination thereof, R a is 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 R b is hydrogen, 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.

13. The semiconductor photoresist composition according to claim 1, wherein: The organometallic compound and the vinyl-containing acid compound are included in a weight ratio of 99:1 to 80:

20.

14. The semiconductor photoresist composition according to claim 1, wherein: The semiconductor photoresist composition further comprises an additive, wherein the additive comprises a surfactant, a cross-linking agent, a leveling agent, an organic acid, a quencher or a combination thereof.

15. A method for forming a pattern, comprising: forming an etching target layer on a substrate; coating the semiconductor photoresist composition according to claim 1 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. 16 . The method of claim 15 , wherein the photoresist pattern is formed using light having a wavelength of 5 nm to 150 nm.

17. The method of claim 15, wherein: The method further includes providing a resist bottom layer formed between the substrate and the photoresist layer.

18. The method of claim 15, wherein: The photoresist pattern has a width of 5 nm to 100 nm.

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