Composition for semiconductor photoresist, and method for forming patterns using the same

Abstract

This invention provides a semiconductor photoresist composition with excellent coating properties and improved sensitivity and pattern roughness, as well as a pattern formation method utilizing the same. [Solution] The present invention relates to a semiconductor photoresist composition comprising an organometallic compound; a compound represented by chemical formula 1; and a solvent, and a pattern formation method utilizing the same. A description of chemical formula 1 is provided in the specification.

Description

Technical Field

[0001] This description relates to a composition for a semiconductor photoresist and a pattern forming method using the same.

Background Art

[0002] As one of the elemental technologies for manufacturing next-generation semiconductor devices, EUV (extreme ultraviolet light) lithography has attracted attention. EUV lithography is a pattern forming technology that uses EUV light with a wavelength of 13.5 nm as an exposure light source. According to EUV lithography, it has been demonstrated that extremely fine patterns (for example, 20 nm or less) can be formed in the exposure process of the semiconductor device manufacturing process.

[0003] The realization of extreme ultraviolet (EUV) lithography requires the development of compatible photoresists that can be performed with spatial resolutions of 16 nm or less. Currently, conventional chemically amplified (CA) photoresists are striving to meet the specifications for resolution, photospeed, and feature roughness, line edge roughness (or LER) for next-generation devices.

[0004] The intrinsic image blur caused by acid-catalyzed reactions in these polymer-type photoresists limits resolution at small feature sizes, a fact long known in electron beam lithography. Chemically amplified (CA) photoresists, while designed for high sensitivity, experience further difficulties, partly under EUV exposure, because their typical elemental makeup lowers the photoresist absorbance at a wavelength of 13.5 nm, resulting in reduced sensitivity.

[0005] CA photoresists also experience difficulties due to roughness issues stemming from their small peach size, and experiments have shown that line edge roughness (LER) increases due to a decrease in photospeed, partly due to the nature of the acid-catalyzed process. Because of the shortcomings and problems of CA photoresists, the semiconductor industry is seeking new types of high-performance photoresists.

[0006] To overcome the shortcomings of the chemically amplified organic photosensitive compositions described above, inorganic photosensitive compositions have been studied. Inorganic photosensitive compositions are mainly used for negative tone patterning, where chemical modification by a non-chemical amplification mechanism is required, and the result is resistant to removal by developer compositions. Inorganic compositions contain inorganic elements that have a higher EUV absorption rate compared to hydrocarbons, ensuring sensitivity even with a non-chemical amplification mechanism, and are not very sensitive to the stochastic effect, resulting in less edge roughness and fewer defects.

[0007] Inorganic photoresists based on tungsten and tungsten peroxopoly acids mixed with niobium, titanium, and / or tantalum have been reported for use as radiation-sensitive materials for patterning (US5061599; H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 495, 298-300, 1986).

[0008] These materials have proven effective in patterning large pitchers in bilayer configurations as deep UV, X-ray, and electron beam sources. More recently, impressive performance has been demonstrated when using cationic hafnium metal oxide sulfate (HfSOx) materials with a peroxo complexing agent to image 15 nm half-pitch (HP) by projection EUV lithography (US2011-0045406; JKStowers, A.Telecky, M.Kocsis, BLClark, DAKEszler, A.Grenville, CNAnderson, PPNaulleau, Proc.SPIE, 7969, 796915, 2011). This system exhibits the best performance of non-CA photoresists and has a light speed close to the requirements for a viable EUV photoresist. However, hafnium metal oxide sulfate materials containing peroxo complexing agents have several practical drawbacks. Firstly, these materials are coated with a highly corrosive sulfuric acid / hydrogen peroxide mixture, resulting in poor shelf-life stability. Secondly, structural modifications to improve performance are not easy as a composite mixture. Thirdly, they must be developed with extremely high concentrations of TMAH (tetramethylammonium hydroxide) solution, such as 25 wt%.

[0009] In recent years, molecules containing tin have been known to exhibit excellent absorption of extreme ultraviolet light, and active research is being conducted on them. In the case of one organotin polymer, the alkyl ligand dissociates due to light absorption or the secondary electrons generated by it, and through crosslinking with surrounding chains via iodine bonds, negative tone patterning that is not removed by organic developers is possible. Such organotin polymers have shown a dramatic improvement in sensitivity while maintaining resolution and line edge roughness, but further improvements to the aforementioned patterning properties are necessary for commercialization. [Overview of the project] [Problems that the invention aims to solve]

[0010] One embodiment provides a semiconductor photoresist composition having excellent coating properties and improved sensitivity and pattern roughness.

[0011] Another embodiment provides a pattern formation method using the semiconductor photoresist composition.

[0012] A semiconductor photoresist composition according to one embodiment comprises an organometallic compound; a compound represented by the following chemical formula 1; and a solvent. [ka]

[0013] In the above chemical formula 1, R 1 These are hydrogen, hydroxyl groups, thiol groups, carboxyl groups, guanidyl groups, amide groups, amino groups, substituted or unsubstituted C1-C20 alkylamine groups, substituted or unsubstituted C6-C20 arylamine groups, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C6-C20 aryl groups, substituted or unsubstituted C2-C20 heteroaryl groups, or combinations thereof. R 2 ~R 4Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C7-C20 arylalkyl group, or a combination thereof. L 1 These are single bonds, or substituted or unsubstituted C1-C10 alkylene groups.

[0014] A pattern formation method according to another embodiment includes the steps of forming an etching target film on a substrate, applying the aforementioned semiconductor photoresist composition on the etching target film to form a photoresist film, patterning the photoresist film to form a photoresist pattern, and etching the etching target film using the photoresist pattern as an etching mask.

[0015] A semiconductor photoresist composition according to one embodiment can provide a photoresist pattern with improved sensitivity, coating properties, and LER characteristics. [Brief explanation of the drawing]

[0016] [Figure 1] This is a cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment. [Modes for carrying out the invention]

[0017] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings. However, in order to clarify the gist of this description, descriptions of functions or configurations that have already been made public will be omitted.

[0018] To clearly explain this description, unnecessary explanatory parts have been omitted, and the same or similar reference numerals are used throughout the specification for identical or similar components. Furthermore, the dimensions and thicknesses of each component shown in the drawings are provided arbitrarily for explanatory purposes, and this description is not necessarily limited to those shown.

[0019] In the drawings, thicknesses were enlarged to clearly represent various layers and regions. Furthermore, in the drawings, the thicknesses of some layers and regions were exaggerated for explanatory purposes. When a layer, film, region, plate, or other part is said to be "on top of" or "on" another part, this includes not only cases where it is "directly on top of" the other part, but also cases where there are other parts in between.

[0020] In this description, "substituted" means that the hydrogen atom is replaced by deuterium, halogen group, hydroxyl group, carboxyl group, thiol group, cyano group, nitro group, -NRR' (where R and R' are each independently hydrogen, a substituted or unsubstituted C1-C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3-C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6-C30 aromatic hydrocarbon group), -SiRR'R'' (where R, R', and R'' are each independently This means that the hydrogen atom is substituted with hydrogen, a substituted or unsubstituted C1-C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3-C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6-C30 aromatic hydrocarbon group, a C1-C30 alkyl group, a C1-C10 haloalkyl group, a C1-C10 alkylsilyl group, a C3-C30 cycloalkyl group, a C6-C30 aryl group, a C1-C20 alkoxy group, a C1-C20 sulfide group, or a combination thereof. "Unsubstituted" means that the hydrogen atom remains a hydrogen atom without being substituted by another substituent.

[0021] In this specification, "alkyl(alkyl) group" means a linear or branched aliphatic hydrocarbon group unless otherwise defined. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0022] The alkyl group may be a C1-C8 alkyl group. For example, the alkyl group may be a C1-C7 alkyl group, a C1-C6 alkyl group, or a C1-C5 alkyl group. For example, the C1-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, or a tert-butyl group or a 2,2-dimethylpropyl group.

[0023] In this document, unless otherwise specified, "cycloalkyl group" refers to a monovalent cyclic aliphatic saturated hydrocarbon group.

[0024] The cycloalkyl group may be a C3-C8 cycloalkyl group, for example, a C3-C7 cycloalkyl group, or a C3-C6 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 to these.

[0025] In this specification, "aryl group" means a substituent in which all elements of the cyclic substituent have p-orbitals, and these p-orbitals form a conjugation, and includes monocyclic or fused polycyclic (i.e., rings that share adjacent pairs of carbon atoms) functional groups.

[0026] In this specification, "heteroaryl group" means an aryl group containing at least one heteroatom selected from the group consisting of N, O, S, P, and Si. Two or more heteroaryl groups can be directly linked through sigma bonds, or, if the heteroaryl group contains two or more rings, the two or more rings can be fused together. If the heteroaryl group is a fused ring, each ring may contain one to three of the heteroatoms.

[0027] A semiconductor photoresist composition according to one embodiment will be described below.

[0028] The semiconductor photoresist composition according to an embodiment of the present invention may include an organometallic compound, a compound represented by the following Chemical Formula 1, and a solvent. [Chemical Formula]

[0029] In Chemical Formula 1, R 1 is hydrogen, a hydroxy group, a thiol group, a carboxyl group, a guanidyl group, an amide group, an amino group, a substituted or unsubstituted C1-C20 alkylamine group, a substituted or unsubstituted C6-C20 arylamine group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C2-C20 heteroaryl group, or a combination thereof, R 2 ~R 4 are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C7-C20 arylalkyl group, or a combination thereof, L 1 is a single bond or a substituted or unsubstituted C1-C10 alkylene group.

[0030] The compound represented by Chemical Formula 1 included in the semiconductor photoresist composition according to the present invention can form an intramolecular chelate by including an amino acid or an amino acid derivative, thereby promoting crosslinking with the organometallic compound, and the sensitivity to extreme ultraviolet rays can be increased with the pattern formed using this.

[0031] In addition, crosslinking is promoted by an amine derivative, and the sensitivity is improved by making the intermolecular bonding smoother by heat treatment after exposure, the adsorption to the substrate is increased, and the surface coating property is improved. <000021​​​This may be hydrogen, a hydroxyl group, a thiol group, a carboxyl group, an amino group, a substituted or unsubstituted C1-C20 alkylamine group, a substituted or unsubstituted C6-C20 arylamine group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C2-C20 heteroaryl group, or a combination thereof.

[0033] As a specific example, R 1 This may be hydrogen, a hydroxyl group, a thiol group, a carboxyl group, an amino group, a substituted or unsubstituted C1-C10 alkylamine group, a substituted or unsubstituted C6-C12 arylamine group, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C12 aryl group, a substituted or unsubstituted C2-C18 heteroaryl group, or a combination thereof.

[0034] For example, the R 1 This may be hydrogen, a hydroxyl group, a thiol group, a carboxyl group, an amino group, a substituted or unsubstituted C1-C10 alkylamine group, a substituted or unsubstituted C6-C12 arylamine group, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted imidazolyl group, or a combination thereof.

[0035] As an example, R 3 and R 4 Each of these may independently be hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C12 aryl group, a substituted or unsubstituted C7-C13 arylalkyl group, or a combination thereof.

[0036] As a specific example, R 3 and R 4 Each of these may independently be hydrogen or a substituted or unsubstituted C1-C10 alkyl group.

[0037] For example, the compound represented by chemical formula 1 is selected from the compounds listed in Group 1 below. [ka]

[0038] The compound represented by chemical formula 1 may be included in an amount of 0.001 to 5% by weight per 100% by weight of the semiconductor photoresist composition.

[0039] For example, the compound represented by chemical formula 1 may be included in an amount of 0.005 to 5% by weight, 0.01 to 5% by weight, or 0.03 to 5% by weight based on 100% by weight of the semiconductor photoresist composition.

[0040] The organometallic compound may be included in an amount of 0.5% to 30% by weight based on 100% by weight of the semiconductor photoresist composition.

[0041] A semiconductor photoresist composition according to one embodiment can improve the sensitivity of a photoresist by containing the compound represented by chemical formula 1 within the specified content range.

[0042] The organometallic compound may also be an organotin compound containing at least one of an organooxy group and an organocarbonyloxy group.

[0043] For example, the organometallic compound is represented by the following chemical formula 2. [ka]

[0044] In the aforementioned chemical formula 2, R 5 These are selected from substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, and substituted or unsubstituted C7-C30 arylalkyl groups. R 6 ~R 8 These are, independently, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C7-C30 arylalkyl groups, alkoxy and aryloxy (-OR) b Here, R b (which are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), carboxyl groups (-O(CO)R c , R c (which is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylamide or dialkylamide (-NR d R e Here, R d and R e Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidato (-NR f (COR g ), here R f and R gEach of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidinato (-NR h C(NR i )R j Here, R h , R i and R j Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (-SR k Here, R k (which is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof) or a thiocarboxyl group (-S(CO)R l , R l (These are hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof.) R 6 ~R 8 At least one of them is an alkoxy and an aryloxy (-OR b Here, R b(which are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), carboxyl groups (-O(CO)R c , R c (which is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylamide or dialkylamide (-NR d R e Here, R d and R e Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidato (-NR f (COR g ), here R f and R g Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidinato (-NR g C(NR h )R i Here, R h , R i and R jEach of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (-SR) k Here, R k (which are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), and thiocarboxyl groups (-S(CO)R l , R l (is selected from hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or a combination thereof).

[0045] The aforementioned R 6 ~R 8 At least one of them is an alkoxy and an aryloxy (-OR b Here, R a (which are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), and carboxyl groups (-O(CO)R c , R c (is selected from hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or a combination thereof).

[0046] On the other hand, the compound represented by chemical formula 2 has -OR as a ligand. b Or -OC(=O)R c By including this, patterns formed using a semiconductor photoresist composition containing it can exhibit excellent limiting resolution.

[0047] Also, -OR b Or -OC(=O)R c The ligand can determine the solubility of the compound represented by chemical formula 2 in a solvent.

[0048] The aforementioned R 5 These are substituted or unsubstituted C1-C8 alkyl groups, substituted or unsubstituted C3-C8 cycloalkyl groups, substituted or unsubstituted C2-C8 aliphatic unsaturated organic groups containing one or more double or triple bonds, substituted or unsubstituted C6-C20 aryl groups, substituted or unsubstituted C4-C20 heteroaryl groups, carbonyl groups, ethoxy groups, propoxy groups, or combinations thereof. R b These are substituted or unsubstituted C1-C8 alkyl groups, substituted or unsubstituted C3-C8 cycloalkyl groups, substituted or unsubstituted C2-C8 alkenyl groups, substituted or unsubstituted C2-C8 alkynyl groups, substituted or unsubstituted C6-C20 aryl groups, or combinations thereof. R c This may be hydrogen, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

[0049] The aforementioned R 5These are methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, prophenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, formyl group, acetyl group, propanoyl group, butanoyl group, pentanoyl group, ethoxy group, propoxy group, or combinations thereof. R b These are ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, prophenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, or combinations thereof. R c This may be hydrogen, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, prophenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, or a combination thereof.

[0050] Furthermore, the organometallic compound is represented by the following chemical formula 3 or chemical formula 4. [ka] In the aforementioned chemical formula 3, R 9 This is a C1-C31 hydrocarbyl group, where 0 <z≦2であり、0<(z+x)≦4であり; [ka] In the aforementioned chemical formula 4, R 10These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 aliphatic unsaturated organic groups containing one or more double or triple bonds, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C4-C30 heteroaryl groups, carbonyl groups, ethylene oxide groups, propylene oxide groups, or combinations thereof. X is sulfur (S), selenium (Se), or tellurium (Te). Y is -OR m Or -OC(=O)R n And, The aforementioned R m These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof. R n This includes hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof. The aforementioned a, b, c, and d are each independent integers between 1 and 20.

[0051] The solvent contained in the semiconductor photoresist composition according to one embodiment may be an organic solvent and may include, but is not limited to, aromatic compounds (e.g., xylene, toluene), alcohols (e.g., 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropyl alcohol, 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), and mixtures thereof.

[0052] In addition to the organometallic compound, the compound represented by chemical formula 1, and the solvent, the semiconductor resist composition according to one embodiment may further contain a resin.

[0053] The aforementioned resin may be a phenolic resin containing at least one of the aromatic molecules listed in Group 2 below. [ka]

[0054] The resin may have a weight-average molecular weight of 500 to 20,000.

[0055] The resin may be included in an amount of 0.1% to 50% by weight relative to the total content of the semiconductor photoresist composition.

[0056] When the aforementioned resin is included within the aforementioned content range, it can have excellent etching resistance and heat resistance.

[0057] On the other hand, the semiconductor photoresist composition is preferably composed of the organometallic compound, the compound represented by chemical formula 1, a solvent, and a resin.

[0058] The semiconductor photoresist composition according to the above-described embodiment may optionally further contain additives. Examples of such additives include surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0059] The surfactant may be, but is not limited to, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts, or combinations thereof.

[0060] Examples of crosslinking agents include, but are not limited to, melamine-based crosslinking agents, substituted urea-based crosslinking agents, acrylic-based crosslinking agents, epoxy-based crosslinking agents, or polymer-based crosslinking agents. Examples of crosslinking agents having at least two crosslinking substituents include compounds such as methoxymethylated glycolyl, butoxymethylated glycolyl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, acrylic methacrylate, 1,4-butanediol diglycidyl ether, glycidol, diglycidyl 1,2-cyclohexanedicarboxylate, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea.

[0061] Leveling agents are used to improve coating flatness during printing, and commercially available, known leveling agents can be used.

[0062] The organic acid may be, but is not limited to, p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, fluorinated sulfonium salts, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or a combination thereof.

[0063] The quencher may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0064] The amount of these additives used can be easily adjusted according to the desired physical properties, and may even be omitted.

[0065] Furthermore, the semiconductor photoresist composition may be further enhanced with a silane coupling agent as an adhesive enhancer to improve adhesion to the substrate (for example, to improve the adhesion of the semiconductor photoresist composition to the substrate). The silane coupling agent may be, but is not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxpropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; or carbon-carbon unsaturated bond-containing silane compounds such as trimethoxy[3-(phenylamino)propyl]silane.

[0066] The semiconductor photoresist composition does not exhibit pattern distortion even when forming patterns with a high aspect ratio. Therefore, it can be used in photoresist processes using light with wavelengths of 5 nm to 150 nm, photoresist processes using light with wavelengths of 5 nm to 100 nm, photoresist processes using light with wavelengths of 5 nm to 80 nm, photoresist processes using light with wavelengths of 5 nm to 50 nm, photoresist processes using light with wavelengths of 5 nm to 30 nm, and photoresist processes using light with wavelengths of 5 nm to 20 nm to form fine patterns with widths of 5 nm to 100 nm, 5 nm to 80 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, and 5 nm to 20 nm. Therefore, by using a semiconductor photoresist composition according to one embodiment, extreme ultraviolet lithography using an EUV light source with a wavelength of approximately 13.5 nm can be realized.

[0067] On the other hand, according to another embodiment, a method for forming a pattern using the semiconductor photoresist composition described above can be provided. For example, the manufactured pattern may be a photoresist pattern.

[0068] A pattern formation method according to one embodiment includes the steps of forming an etching target film on a substrate, applying the aforementioned semiconductor photoresist composition on the etching target film to form a photoresist film, patterning the photoresist film to form a photoresist pattern, and etching the etching target film using the photoresist pattern as an etching mask.

[0069] The following describes a method for forming a pattern using the semiconductor photoresist composition described above, with reference to Figure 1. Figure 1 is a cross-sectional view illustrating a pattern formation method using the semiconductor photoresist composition according to the present invention.

[0070] Referring to Figure 1(a), first, the object to be etched is prepared. An example of the object to be etched may be a thin film 102 formed on a semiconductor substrate 100. The following explanation will only cover the case where the object to be etched is a thin film 102. To remove contaminants and other materials remaining on the thin film 102, the surface of the thin film 102 is cleaned. The thin film 102 may be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film.

[0071] Next, a resist underlayer forming composition for forming a resist underlayer 104 is coated onto the surface of the cleaned thin film 102 using a spin coating method. However, this embodiment is not necessarily limited to this, and various known coating methods, such as spray coating, dip coating, knife-edge coating, printing methods, such as inkjet printing and screen printing, can also be used.

[0072] The resist underlayer coating process can be omitted, and the case where the resist underlayer is coated will be described below.

[0073] Subsequently, drying and baking processes are performed to form a resist underlayer film 104 on the thin film 102. The baking process is carried out at approximately 100 to 500°C, for example, at approximately 100°C to 300°C.

[0074] The resist underlayer 104 is formed between the substrate 100 and the photoresist film 106. This prevents the scattering of irradiation lines reflected from the interface between the substrate 100 and the photoresist film 106 or from the interlayer hard mask in unintended photoresist regions, thereby preventing non-uniformity of the photoresist linewidth and interference with pattern formation.

[0075] Referring to Figure 1(b), the above-mentioned semiconductor photoresist composition is coated onto the resist underlayer film 104 to form a photoresist film 106. The photoresist film 106 may also be formed by coating the above-mentioned semiconductor photoresist composition onto a thin film 102 formed on the substrate 100 and then curing it through a heat treatment process.

[0076] More specifically, the step of forming a pattern using a semiconductor photoresist composition may include the steps of applying the above-described semiconductor photoresist composition onto a substrate 100 on which a thin film 102 is formed by spin coating, slit coating, inkjet printing, etc., and drying the applied semiconductor photoresist composition to form a photoresist film 106.

[0077] Since the compositions for semiconductor photoresists have already been explained in detail, we will omit any redundant explanations.

[0078] Next, a first baking step is performed in which the substrate 100 on which the photoresist film 106 is formed is heated. The first baking step can be performed at a temperature of approximately 80°C to approximately 120°C.

[0079] Referring to Figure 1(c), the photoresist film 106 is selectively exposed using a patterned mask 110.

[0080] For example, examples of light that can be used in the exposure process include not only light such as activated irradiation luminance i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm), and ArF excimer laser (wavelength 193nm), but also light with high energy wavelengths such as EUV (Extreme Ultra Violet; wavelength 13.5nm) and E-Beam (electron beam).

[0081] More specifically, the exposure light according to one embodiment may be light having a wavelength range of 5 nm to 150 nm, or it may be light having a high energy wavelength such as EUV (Extreme Ultra Violet; wavelength 13.5 nm) or E-Beam (electron beam).

[0082] The exposed region 106b of the photoresist film 106 forms a polymer through crosslinking reactions such as condensation between organometallic compounds, thereby acquiring different solubility from the unexposed region 106a of the photoresist film 106.

[0083] Next, a second baking process is performed on the substrate 100. The second baking process can be carried out at a temperature of approximately 90°C to approximately 200°C. By performing the second baking process, the exposed region 106b of the photoresist film 106 becomes difficult to dissolve in the developer.

[0084] Figure 1(d) shows a photoresist pattern 108 formed by dissolving and removing the photoresist film 106a corresponding to the unexposed region using a developer. Specifically, the photoresist pattern 108 corresponding to the negative tone image is completed by dissolving the photoresist film 106a corresponding to the unexposed region using an organic solvent such as 2-heptanone, and then removing it.

[0085] As mentioned above, the developer used in the pattern-forming method according to one embodiment may be an organic solvent. Examples of organic solvents used in the pattern-forming method according to one embodiment include ketones such as methyl ethyl ketone, acetone, cyclohexanone, and 2-heptanone; alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, and methanol; esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, and butyrolactone; aromatic compounds such as benzene, xylene, and toluene; or combinations thereof.

[0086] However, the photoresist pattern according to one embodiment is not necessarily limited to being formed as a negative tone image, and may be formed to have a positive tone image. In this case, examples of developers that can be used to form a positive tone image include quaternary ammonium hydroxide compositions such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof.

[0087] As mentioned above, the photoresist pattern 108 formed by exposure with light having wavelengths such as i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm), and ArF excimer laser (wavelength 193nm), as well as high-energy light such as EUV (Extreme Ultra Violet; wavelength 13.5nm) and E-Beam (electron beam), can have a thickness width of 5nm to 100nm. For example, the photoresist pattern 108 can be formed with thickness widths of 5nm to 90nm, 5nm to 80nm, 5nm to 70nm, 5nm to 60nm, 5nm to 50nm, 5nm to 40nm, 5nm to 30nm, and 5nm to 20nm.

[0088] On the other hand, the photoresist pattern 108 can have a half-pitch of about 50 nm or less, for example 40 nm or less, for example 30 nm or less, for example 20 nm or less, for example 15 nm or less, and a pitch having a line width roughness of about 10 nm or less, about 5 nm or less, about 3 nm or less, or about 2 nm or less.

[0089] Next, the photoresist pattern 108 is used as an etching mask to etch the resist underlayer film 104. The organic film pattern 112 is formed by the etching process described above. The formed organic film pattern 112 can also have a width corresponding to the photoresist pattern 108.

[0090] Referring to Figure 1(e), the photoresist pattern 108 is applied as an etching mask to etch the exposed thin film 102. As a result, the thin film is formed as a thin film pattern 114.

[0091] The thin film 102 can be etched, for example, by dry etching using an etching gas, and the etching gas can be, for example, CHF3, CF4, Cl2, BCl3, or a mixture thereof.

[0092] The thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process using an EUV light source in the preceding exposure process can have a width corresponding to the photoresist pattern 108. For example, it can have a width of 5 nm to 100 nm, similar to the photoresist pattern 108. For instance, the thin film pattern 114 formed by the exposure process using an EUV light source can have widths of 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, and 5 nm to 20 nm, similar to the photoresist pattern 108, and more specifically, it can be formed with a width of 20 nm or less. [Examples]

[0093] The present invention will be described in more detail below through the examples relating to the manufacture of the semiconductor photoresist composition described above. However, the technical features of the present invention are not limited by the following examples.

[0094] Synthesis of organometallic compounds Synthesis Example 1 Add 310 g of t-butylSn(Dimethylamine) and 50 ml of anhydrous pentane to a 250 ml round-bottom flask, and while maintaining the temperature at 0°C, add 20 g of propionic acid and stir at room temperature for 6 hours. Once the reaction is complete, filter, concentrate, and vacuum dry to obtain the compound represented by the following chemical formula 5. [ka]

[0095] Synthesis Example 2 Add 310 g of t-butylSn(Dimethylamine) and 50 ml of anhydrous pentane to a 250 mL round-bottom flask, and while maintaining the temperature at 0°C, add 20 g of MIBC and stir at room temperature for 6 hours. Once the reaction is complete, filter, concentrate, and vacuum dry to obtain the compound represented by the following chemical formula 6. [ka]

[0096] Synthesis Example 3 After dissolving 10 g of dibutyltin dichloride in 30 mL of ether, 70 mL of 1 M sodium hydroxide (NaOH) aqueous solution is added and the mixture is stirred for 1 hour. After stirring, the resulting solid is filtered and washed three times with 25 mL of deionized water, and then dried under reduced pressure at 100°C to obtain an organometallic compound with a weight-average molecular weight of 1,500 represented by the following chemical formula 7. [ka]

[0097] (Manufacturing of semiconductor photoresist compositions) Examples 1-14 and Comparative Examples 1-4 The organometallic compounds obtained in Synthesis Examples 1 to 3 were each dissolved in 3% Propylene glycol methyl ether acetate (PGMEA), and amino acid compounds or organic acid compounds C1 to C5 were added and dissolved at the concentrations listed in Table 1 below. The mixture was then filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to produce the semiconductor photoresist compositions according to the examples and comparative examples. After coating a silicon wafer with the composition to a thickness of 240 Å, a patterned film was produced through PAB, exposure, PEB, and development processes.

[0098] [Table 1]

[0099] C1: Glycine C2: Risine C3: Histidine C4:N-ethylglycine C5: Glutaric acid

[0100] Evaluation 1: Evaluation of sensitivity and line edge roughness (LER) The photoresist compositions according to the above examples and comparative examples were spin-coated onto a 200 mm circular silicon wafer whose surface was deposited with HMDS at 1500 rpm for 30 seconds, baked at 110°C for 60 seconds (post-apply bake, PAB), and then left at room temperature (23±2°C) for 30 seconds.

[0101] Subsequently, a linear array of 50 circular pads with a diameter of 500 μm was projected onto a wafer coated with the photoresist composition using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). The pad exposure time was adjusted to ensure that the increasing EUV dose was applied to each pad.

[0102] Subsequently, the resist and substrate were exposed on a hot plate at 160°C for 120 seconds and then fired. The fired film was developed with PGMEA solvent to form a negative tone image. Finally, the process was completed by firing on a hot plate at 150°C for 2 minutes.

[0103] The residual resist thickness of the exposed pads was measured using a polarization measurement method (Ellipsometer). The remaining thickness was measured for each exposure level and graphed as a function of the exposure level. Sensitivity was measured, and the LER was measured from the FE-SEM images. The results are shown in Tables 2 to 4.

[0104] Evaluation 2: Coating characteristics evaluation The photoresist compositions according to Examples 1-14 and Comparative Examples 1-4 were spin-coated onto wafers at 1500 rpm for 60 seconds, and then fired at 110°C for 60 seconds to form thin films. The surface roughness of the thin films was then measured using software (e.g., optical profiler) from images taken with an atomic force microscope (AFM) according to the following criteria, and the results are shown in Tables 2-4.

[0105] Among surface roughness measurements, root mean square roughness (Rq) refers to the root mean square (rms) of the vertical values ​​within the reference length of the profile.

[0106] [Evaluation Criteria] -◎: Rq 0.3nm or less, -○: Rq more than 0.3nm, less than 0.4nm, -×: Rq over 0.4nm

[0107] [Table 2]

[0108] [Table 3]

[0109] [Table 4]

[0110] From the results in Tables 2 to 4, it can be confirmed that the photoresist compositions for semiconductors according to Examples 1 to 14 maintain excellent sensitivity and LER characteristics and exhibit significantly superior coating characteristics compared to Comparative Examples 1 to 4.

[0111] Although specific embodiments of the present invention have been described and illustrated above, it is obvious to those ordinary skill in the art that the present invention is not limited to the described embodiments and can be modified and transformed in various ways without departing from the spirit and scope of the invention. Therefore, such modifications or variations should not be understood individually from the technical spirit or viewpoint of the present invention, and the modified embodiments should be considered to fall within the scope of the claims of the present invention. [Explanation of Symbols]

[0112] 100...Substrate, 102...Thin film, 104...Resist underlayer film, 106...Photoresist film, 106a...Unexposed region, 106b...Exposed region, 108...Photoresist pattern, 112...Organic film pattern, 110...Patterned mask, 114...Thin film pattern.

Claims

1. Organometallic compounds; Compounds represented by the following chemical formula 1; and solvent A composition for semiconductor photoresists, including: 【Chemistry 1】 In the aforementioned chemical formula 1, R １ These are hydrogen, a hydroxyl group, a thiol group, a carboxyl group, a guanidyl group, an amide group, an amino group, a substituted or unsubstituted C1-C20 alkylamine group, a substituted or unsubstituted C6-C20 arylamine group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C2-C20 heteroaryl group, or a combination thereof. R ２ ~R ４ Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C7-C20 arylalkyl group, or a combination thereof. L １ These are single bonds, or substituted or unsubstituted C1-C10 alkylene groups.

2. The aforementioned R １ The semiconductor photoresist composition according to claim 1, wherein is a hydrogen, hydroxyl group, thiol group, carboxyl group, amino group, substituted or unsubstituted C1-C10 alkylamine group, substituted or unsubstituted C6-C12 arylamine group, substituted or unsubstituted C1-C10 alkyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted indolyl group, substituted or unsubstituted imidazolyl group, or a combination thereof.

3. The aforementioned R ３ and R ４ The semiconductor photoresist composition according to claim 1, wherein each is independently hydrogen or a substituted or unsubstituted C1-C10 alkyl group.

4. The semiconductor photoresist composition according to claim 1, wherein the compound represented by the chemical formula 1 is one selected from the compounds listed in Group 1 below: 【Chemistry 2】

5. The semiconductor photoresist composition according to claim 1, wherein the compound represented by chemical formula 1 is contained in an amount of 0.001 to 5% by weight based on 100% by weight of the semiconductor photoresist composition.

6. The semiconductor photoresist composition according to claim 1, wherein the organometallic compound is contained in an amount of 0.5% to 30% by weight based on 100% by weight of the semiconductor photoresist composition.

7. The semiconductor photoresist composition according to claim 1, further comprising an additive of a surfactant, a crosslinking agent, a leveling agent, an organic acid, an inhibitor (quencher), or a combination thereof.

8. The semiconductor photoresist composition according to claim 1, wherein the organometallic compound is an organotin compound containing at least one of an organic oxy group and an organic carbonyl oxy group.

9. The organometallic compound is represented by the following chemical formula 2, and is the semiconductor photoresist composition according to claim 1: 【Transformation 3】 In the aforementioned chemical formula 2, R ５ These are selected from substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, and substituted or unsubstituted C7-C30 arylalkyl groups. R ６ ~R ８ are each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, an alkoxy and an aryloxy (—OR ｂ , where R ｂ is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), a carboxyl group (—O(CO)R ｃ , R ｃ is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an alkylamide or a dialkylamide (—NR ｄ R ｅ , where R ｄ and R ｅ are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an amidato (—NR ｆ (COR ｇ ), where R ｆ and R ｇ are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an amidinato (—NR ｈ C (NR ｉ ) R ｊ Here, R ｈ , R ｉ and R ｊ Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (-SR ｋ Here, R ｋ (which is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), or a thiocarboxyl group (-S(CO)R ｌ , R ｌ (These are hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof.) R ６ ~R ８ At least one of them is an alkoxy and an aryloxy (-OR ｂ Here, R ｂ (These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), carboxyl groups (-O(CO)R ｃ , R ｃ (-NR) ｄ R ｅ Here, R ｄ and R ｅ Each is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidato (-NR ｆ (COR ｇ ), here R ｆ and R ｇ Each is independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidinato (-NR ｇ C (NR ｈ ) R ｉ Here, R ｈ , R ｉ and R ｊ Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (-SR ｋ Here, R ｋ (which are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), and thiocarboxyl groups (-S(CO)R ｌ , R ｌ (These are selected from hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof.)

10. The aforementioned R ６ ~R ８ At least one of them is an alkoxy and an aryloxy (-OR ｂ Here, R ａ (which are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), and carboxyl groups (-O(CO)R ｃ , R ｃ The semiconductor photoresist composition according to claim 9, wherein is selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof.

11. The aforementioned R ５ These are substituted or unsubstituted C1-C8 alkyl groups, substituted or unsubstituted C3-C8 cycloalkyl groups, substituted or unsubstituted C2-C8 aliphatic unsaturated organic groups containing one or more double or triple bonds, substituted or unsubstituted C6-C20 aryl groups, substituted or unsubstituted C4-C20 heteroaryl groups, carbonyl groups, ethoxy groups, propoxy groups, or combinations thereof. The aforementioned R ｂ These are substituted or unsubstituted C1-C8 alkyl groups, substituted or unsubstituted C3-C8 cycloalkyl groups, substituted or unsubstituted C2-C8 alkenyl groups, substituted or unsubstituted C2-C8 alkynyl groups, substituted or unsubstituted C6-C20 aryl groups, or combinations thereof. The aforementioned R ｃ The semiconductor photoresist composition according to claim 10, wherein is hydrogen, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

12. The organometallic compound is represented by the following chemical formula 3 or chemical formula 4, and is part of the semiconductor photoresist composition according to claim 1: 【Chemistry 4】 In the aforementioned chemical formula 3, R ９ is a C1-C31 hydrocarbyl group, where 0 < z ≤ 2 and 0 < (z + x) ≤ 4; 【Transformation 5】 In the aforementioned chemical formula 4, R １０ These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 aliphatic unsaturated organic groups containing one or more double or triple bonds, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C4-C30 heteroaryl groups, carbonyl groups, ethylene oxide groups, propylene oxide groups, or combinations thereof. X is sulfur (S), selenium (Se), or tellurium (Te), Y is -OR ｍ or -OC(=O)R ｎ And, The aforementioned R ｍ These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof. R ｎ These are hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof. The terms a, b, c, and d are each independent integers between 1 and 20.

13. Steps include forming an etching target film on a substrate; A step of forming a photoresist film by applying the semiconductor photoresist composition according to any one of claims 1 to 12 onto the film to be etched; Steps of patterning the photoresist film to form a photoresist pattern; and A pattern formation method comprising the step of etching the film to be etched using the aforementioned photoresist pattern as an etching mask.

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