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

Abstract

The present invention provides a semiconductor photoresist composition with excellent sensitivity, improved storage stability and coating properties, and a pattern formation method using the semiconductor photoresist composition. [Solution] A semiconductor photoresist composition comprising an organometallic compound; compound A represented by the following chemical formula 1 or chemical formula 2; and a solvent, and a pattern formation method using the same. The definitions of chemical formulas 1 and 2 are as described herein. JPEG2026112423000028.jpg76170

Description

[Technical Field]

[0001] This document describes a composition for semiconductor photoresists and a method for forming patterns using the same. [Background technology]

[0002] EUV (extreme ultraviolet) lithography is attracting attention as one of the key technologies for manufacturing next-generation semiconductor devices. EUV lithography is a pattern formation technique that uses EUV light with a wavelength of 13.5 nm as the exposure light source. It has been demonstrated that EUV lithography can form extremely fine patterns (for example, less than 20 nm) in the exposure process of semiconductor device manufacturing.

[0003] Performing extreme ultraviolet (EUV) lithography requires the development of compatible photoresists that can be performed at spatial resolutions of 16 nm or less. Currently, traditional chemically amplified (CA) photoresists are striving to meet the specifications for resolution, photospeed, feature roughness, and line edge roughness (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 are designed for high sensitivity, but their typical elemental makeup lowers the absorbance of the photoresists at a wavelength of 13.5 nm, resulting in reduced sensitivity, which can make them partially more difficult to work with under EUV exposure.

[0005] CA photoresists also face challenges due to roughness issues at small feature sizes, 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. These drawbacks and problems with CA photoresists have led to a demand in the semiconductor industry for new types of high-performance photoresists.

[0006] To overcome the shortcomings of the aforementioned chemically amplified organic photosensitive compositions, inorganic photosensitive compositions have been studied. Inorganic photosensitive compositions are mainly used for negative tone patterning, where chemical modification by non-chemical amplification mechanisms is required, and the resulting pattern is resistant to removal by developer compositions. Inorganic compositions contain inorganic elements that have a higher EUV absorption rate compared to hydrocarbons, and sensitivity can be ensured even with non-chemical amplification mechanisms. They are also less sensitive to the stochastic effect, and are known to have lower line edge roughness and defect counts.

[0007] Inorganic photoresists based on tungsten and tungsten peroxopolyacids 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, 49(5), 298-300, 1986).

[0008] These materials have proven effective for patterning large features 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 that approaches 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 they are composite mixtures. Thirdly, they should be developed with extremely high concentrations of TMAH (tetramethylammonium hydroxide) solutions, such as 25 wt%.

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

[0010] The present invention provides a semiconductor photoresist composition with excellent sensitivity, improved storage stability, and improved coating properties. Furthermore, the present invention provides a pattern formation method using the aforementioned semiconductor photoresist composition. [Means for solving the problem]

[0011] The semiconductor photoresist composition of the present invention comprises an organometallic compound; compound A represented by the following chemical formula 1 or chemical formula 2; and a solvent:

[0012] [ka] In the aforementioned chemical formula 1, X 1 and X 2 Each of these is independently a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C3 to C20 heteroaryl group, or a substituted or unsubstituted C6 to C20 aryl group, or the aforementioned X 1and X 2 are connected to each other to form a single or multiple rings:

[0013] [Chemical formula] In Chemical formula 2, M 1 is -C(=O)-, -O-, -S-, -N(-L x -R x )-(where L x is a single bond or a substituted or unsubstituted C1 to C5 alkylene group, and R x is hydrogen, a carboxyl group, or a substituted or unsubstituted C1 to C5 alkyl group), or a combination thereof, L 1 and L 2 are each independently a single bond or a substituted or unsubstituted C1 to C5 alkylene group, Z 1 and Z 2 are each independently a hydroxy group, a halogen, a cyano group, a cyano-containing group, an ammonium group, an amide group, a nitro group, a carboxyl group, an ester group, a sulfone group, a sulfonate group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, or a combination thereof, n 1 and n 2 are each independently one of the integers from 0 to 4.

[0014] The composition for a semiconductor photoresist of the present invention is excellent in sensitivity, storage stability, and coating property, and can precisely control a small-sized pattern therefrom, and can achieve excellent resolution. [Brief Description of Drawings]

[0015] [Figure 1]This is a cross-sectional view illustrating a pattern formation method using the semiconductor photoresist composition of the present invention. [Modes for carrying out the invention]

[0016] 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, explanations of known functions or configurations will be omitted.

[0017] To ensure clarity in this description, irrelevant details 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 the components shown in the drawings are provided arbitrarily for illustrative purposes and are not necessarily limited to those depicted.

[0018] In the drawings, thicknesses were enlarged to clearly represent various layers and regions. Furthermore, for the sake of clarity in the drawings, the thicknesses of some layers and regions were exaggerated. When a layer, film, region, plate, or other part is said to be "on top of" another part, this includes not only cases where it is "directly on top" of the other part, but also cases where another part lies in between.

[0019] 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' (wherein R and R' are independently hydrogen, a substituted or unsubstituted C1-C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3-C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6-C30 aromatic hydrocarbon group), -SiRR'R'' (wherein R, R', and R'' are independently hydrogen, This means that the group is substituted with a C1-C30 saturated or unsaturated aliphatic hydrocarbon group, a C3-C30 saturated or unsaturated alicyclic hydrocarbon group, or a C6-C30 aromatic hydrocarbon group (which is a substituted or unsubstituted 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 as a hydrogen atom without being replaced by another substituent.

[0020] 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.

[0021] 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, or a tert-butyl group or a 2,2-dimethylpropyl group.

[0022] In this document, "cycloalkyl group" refers to a monovalent cyclic aliphatic saturated hydrocarbon group unless otherwise defined.

[0023] The cycloalkyl group may be a C3 to C8 cycloalkyl group, for example, a C3 to C7 cycloalkyl group, or a C3 to C6 cycloalkyl group. For example, the cycloalkyl group may be, but is not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

[0024] 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 separate adjacent pairs of carbon atoms) functional groups.

[0025] In this specification, a "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 may be directly linked via sigma bonds, or, if the heteroaryl group contains two or more rings, the two or more rings may be fused together. If the heteroaryl group is a fused ring, each ring may contain one to three of the heteroatoms.

[0026] In this specification, "alkenyl group" means an aliphatic unsaturated alkenyl group containing one or more double bonds, whether linear or branched aliphatic hydrocarbon group.

[0027] In this specification, "alkynyl group" means an aliphatic unsaturated alkynyl group containing one or more triple bonds, whether a linear or branched aliphatic hydrocarbon group.

[0028] The following describes a semiconductor photoresist composition according to one embodiment.

[0029] The semiconductor photoresist composition of this embodiment may contain: an organometallic compound; compound A represented by the following chemical formula 1 or chemical formula 2; and a solvent: [ka]

[0030] In the aforementioned chemical formula 1, X 1 and X 2 Each of these is independently a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C3 to C20 heteroaryl group, or a substituted or unsubstituted C6 to C20 aryl group, or the aforementioned X 1 and X 2 These are connected to each other to form one or more rings: [ka]

[0031] In the aforementioned chemical formula 2, M 1 -C(=O)-, -O-, -S-, -N(-L x -R x )-(Here, L x R is a single bonded, substituted, or unsubstituted C1 to C5 alkylene group, x (is hydrogen, a carboxyl group, or a substituted or unsubstituted C1-C5 alkyl group), or a combination thereof. L 1 and L 2 Each of these is independently a single bonded, substituted, or unsubstituted C1 to C5 alkylene group. Z 1 and Z 2Each of these is independently a hydroxyl group, halogen, cyano group, cyano-containing group, ammonium group, amide group, nitro group, carboxyl group, ester group, sulfone group, sulfonate group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, or a combination thereof. n 1 and n 2 Each of these is independently one of the integers between 0 and 4.

[0032] The compound shown in Chemical Formula 1 has two adjacent carbonyl groups (-C=O-) linked together, and can act as a chelate ligand that weakly links the tin (Sn) groups of the organometallic compounds in the composition. The compound shown in Chemical Formula 2 also contains a carbonyl group (-C=O-) and can act as a bridging ligand between the tin (Sn) groups of the organometallic compounds in the composition. Therefore, the semiconductor photoresist composition of this embodiment, which includes the compound shown in Chemical Formula 1 or Chemical Formula 2 (i.e., compound A), can achieve improved coating properties and sensitivity, as well as improved line etching roughness (LWR), resulting in excellent pattern formation.

[0033] The compounds represented by chemical formula 1 and chemical formula 2 (i.e., compound A) contain heteroatoms with relatively high electronegativity, and therefore can act as ligands for coordination bonding with metals or metal cations. Furthermore, compound A can be cyclic, and cyclic compounds have relatively restricted molecular morphology and can have lower entropy compared to low-linear compounds, thus increasing their bonding strength with metals.

[0034] If compound A is a cyclic compound and contains heteroatoms in the ring, compound A can act as a competitive inhibitor of the reaction between the solvent and the metal cation in the composition, further improving the storage stability of the composition. Furthermore, compound A can promote the reaction of the organometallic compound in the exposed region, reducing the amount of composition required for pattern formation, while also reducing the degree of crosslinking of the organometallic compound in the non-exposed region, thereby enabling stable pattern formation during the exposure process.

[0035] In the above chemical formula 1, X 1 and X 2 Each of these is independently a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group, or the aforementioned X 1 and X 2 These can be linked together to form one or more rings, for example, substituted or unsubstituted C1 to C20 alkoxy groups, substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C3 to C10 cycloalkyl groups, substituted or unsubstituted C6 to C20 aryl groups, or a combination thereof. 1 and X 2 These can be connected to each other to form one or more rings.

[0036] X of the aforementioned chemical formula 1 1 and X 2 For example, each independently is a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, and the X 1 and X 2At least one of these may be a substituted or unsubstituted C6 to C20 aryl group. The substituted or unsubstituted C1 to C20 alkoxy group may be a substituted or unsubstituted methoxy group or a substituted or unsubstituted ethoxy group, and the substituted or unsubstituted C6 to C20 aryl group may be a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group.

[0037] X of the aforementioned chemical formula 1 1 and X 2 Each of these is independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, and the X 1 and X 2 These can be connected to each other to form one or more rings. For example, X 1 and X 2 X is a phenyl group, and any one carbon of each phenyl group can be linked to form a ring. Another example is X 1 and X 2 Any one of them is a substituted or unsubstituted cycloalkyl group, and any one of them is a substituted or unsubstituted alkyl group, and the cycloalkyl group and any one of the alkyl groups can be linked to form multiple rings.

[0038] The compound represented by chemical formula 1 may be, for example, one or more compounds selected from the following group 1: [ka]

[0039] In the aforementioned chemical formula 2, M 1 -C(=O)-, -O-, -S-, -N(-L x -R x )-(Here, L x R is a single bonded, substituted, or unsubstituted C1 to C5 alkylene group,x A (where C1-C5 alkyl group is hydrogen, a carboxyl group, or a substituted or unsubstituted C1-C5 alkyl group), or a combination thereof, for example, -C(=O)-, -O-, -S-, -N(-L x -R x )-(Here, L x R is a single bond or a methylene group. x (These are hydrogen, a carboxyl group, or a methyl group), or a combination thereof.

[0040] In the aforementioned chemical formula 2, L 1 and L 2 Each of these is independently a single-bonded, substituted, or unsubstituted C1 to C5 alkylene group, which may be, for example, a single bond or a methylene group.

[0041] In the above chemical formula 2, Z 1 and Z 2 Each of these is independently a hydroxyl group, a halogen, a carboxyl group, an ester group, a sulfone group, a sulfonate group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, or a combination thereof, for example a hydroxyl group, a halogen, a carboxyl group, an ester group, a sulfone group, a sulfonate group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C2 to C20 alkenyl group, for example a halogen, a carboxyl group, a sulfonate group, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C1 to C20 alkyl group.

[0042] In the above chemical formula 2, n1 and n2 are one integer from 0 to 4, for example, one integer from 0 to 3, and one integer from 0 to 2, for example, 0 or 1.

[0043] The compound represented by chemical formula 2 may be one or more compounds selected from the following group 2: [ka]

[0044] Compound A, represented by chemical formula 1 or chemical formula 2, may be included in an amount of 0.01% to 5% by weight, 0.02% to 5% by weight, 0.03% to 5% by weight, or 0.05% to 5% by weight, based on 100% by weight of the semiconductor photoresist composition. When compound A, represented by chemical formula 1 or chemical formula 2, is included within the above content range, the storage stability and sensitivity of the composition can be further improved.

[0045] The organometallic compound may be present in an amount of 0.5% to 30% by weight relative to 100% by weight of the semiconductor photoresist composition. In the semiconductor photoresist composition of this embodiment, the organometallic compound may be present in an amount of 0.5% to 30% by weight, for example, 1% to 30% by weight, for example, 1% to 25% by weight, for example, 1% to 20% by weight, for example, 1% to 15% by weight, for example, 1% to 10% by weight, for example, 1% to 5% by weight, based on 100% by weight of the semiconductor photoresist composition.

[0046] The semiconductor photoresist composition of this embodiment can improve the sensitivity of the photoresist by containing the organometallic compound within the specified content range.

[0047] The organometallic compound may be an organotin compound containing at least one of an organic oxy group and an organic carbonyl oxy group.

[0048] The organometallic compound can be represented by the following chemical formula 3: [ka]

[0049] In the aforementioned chemical formula 3, R 1 These are selected from substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C3 to C20 cycloalkyl groups, substituted or unsubstituted C2 to C20 alkenyl groups, substituted or unsubstituted C2 to C20 alkynyl groups, substituted or unsubstituted C6 to C30 aryl groups, and substituted or unsubstituted C7 to C30 arylalkyl groups. R 2 R4 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 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 or an acyloxy group (-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 eEach 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), amidinate (-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 lis hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), and R 2 to R 4 at least one of which is alkoxy and 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 or an acyloxy 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 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), amidinate (-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 are substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C3 to C20 cycloalkyl groups, substituted or unsubstituted C2 to C20 alkenyl groups, substituted or unsubstituted C2 to C20 alkynyl groups, substituted or unsubstituted C6 to C30 aryl groups, or combinations thereof), and thiocarboxyl groups (-S(CO)R l , R l (is selected from hydrogen, substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C3 to C20 cycloalkyl groups, substituted or unsubstituted C2 to C20 alkenyl groups, substituted or unsubstituted C2 to C20 alkynyl groups, substituted or unsubstituted C6 to C30 aryl groups, or a combination thereof.)

[0050] The aforementioned R 2 ~R 4 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 and acyloxy groups (-O(CO)R c , R c (These may be 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.)

[0051] On the other hand, the compound represented by chemical formula 3 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.

[0052] Also, -OR b Or -OC(=O)R c The ligand can determine the solubility of the compound represented by chemical formula 3 in a solvent.

[0053] The aforementioned R 1 These are selected from substituted or unsubstituted C1 to C8 alkyl groups, substituted or unsubstituted C3 to C8 cycloalkyl groups, substituted or unsubstituted C2 to C8 alkenyl groups, substituted or unsubstituted C2 to C8 alkynyl groups, substituted or unsubstituted C6 to C20 aryl groups, and substituted or unsubstituted C7 to C20 arylalkyl groups. R bThese 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 can 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.

[0054] The aforementioned R 1 These 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, propenyl group, butenyl group, ethynyl group, propanyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl 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, propenyl group, butenyl group, ethynyl group, propanyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, or combinations thereof. R c This can 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, propenyl group, butenyl group, ethynyl group, propanyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, or a combination thereof.

[0055] Furthermore, the organometallic compound can be represented by the following chemical formula 4 or chemical formula 5. [ka] In the aforementioned chemical formula 4, R 5 These are the C1 to C31 hydrocarbyl group, where 0 <z≦2であり、0<(z+x)≦4であり; [ka] In the aforementioned chemical formula 5, R 6 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 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 terms a, b, c, and d are each independent integers between 1 and 20.

[0056] In addition to the organometallic compound, compound A represented by chemical formula 1 or chemical formula 2, and solvent, the semiconductor resist composition of this embodiment may further contain a resin.

[0057] The aforementioned resin may be a phenolic resin containing at least one aromatic moisture listed in Group 3 below. [ka]

[0058] The resin may have a weight-average molecular weight of 500 g / mol to 20,000 g / mol.

[0059] On the other hand, the semiconductor photoresist composition preferably comprises the aforementioned organometallic compound, compound A represented by chemical formula 1 or chemical formula 2, a solvent, and a resin.

[0060] The solvent contained in the semiconductor photoresist composition of this 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.

[0061] The semiconductor photoresist compositions according to the above-described embodiments may optionally further contain additives. Examples of such additives include surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0062] The surfactant may be, but is not limited to, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts, or combinations thereof.

[0063] Examples of crosslinking agents include, but are not limited to, melamine-based crosslinking agents, substitution element-based crosslinking agents, acrylic-based crosslinking agents, epoxy-based crosslinking agents, or polymer-based crosslinking agents. Crosslinking agents having at least two crosslinking substituents can be used, such as compounds like 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-cyclohexane dicarboxylate, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated elements, butoxymethylated elements, or methoxymethylated thio elements.

[0064] Leveling agents are used to improve the flatness of the coating during printing, and commercially available, known leveling agents can be used.

[0065] Organic acids may include, but are not limited to, p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, sulfonium fluoride salts, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycophosphate, succinic acid, or combinations thereof.

[0066] The quencher may be diphenyl(p-toluyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0067] The amount of these additives used can be easily adjusted according to the desired physical properties, and they can also be omitted.

[0068] Furthermore, the semiconductor photoresist composition may be further enhanced with a silane coupling agent as an adhesive strengthening agent to improve adhesion to the substrate (for example, to improve the adhesion strength 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.

[0069] The semiconductor photoresist composition may 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, 5 nm to 100 nm, 5 nm to 70 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, or 5 nm to 20 nm to form fine patterns, for example, fine patterns with a width of 5 nm to 100 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, or 5 nm to 20 nm. Therefore, by using the semiconductor photoresist composition of this embodiment, extreme ultraviolet lithography using an EUV light source with a wavelength of approximately 13.5 nm can be realized.

[0070] On the other hand, according to other embodiments, a method for forming a pattern using the aforementioned semiconductor photoresist composition can be provided. For example, the manufactured pattern may be a photoresist pattern.

[0071] The pattern formation method of this embodiment includes the steps of forming an etching target film on a substrate, applying the above-mentioned 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.

[0072] The method for forming a pattern using the aforementioned semiconductor photoresist composition will be described below with reference to Figure 1. Figure 1 is a cross-sectional view illustrating the pattern formation method using the semiconductor photoresist composition according to the present invention.

[0073] Referring to Figure 1(a), the first step is to provide an object to be etched. An example of the object to be etched is a thin film 102 formed on a semiconductor substrate 100. The following explanation will be limited to the case where the object to be etched is a thin film 102. To remove contaminants and other substances 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.

[0074] 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, the embodiment is not necessarily limited thereto, and various known coating methods, such as spray coating, dip coating, knife-edge coating, and printing methods, such as inkjet printing and screen printing, can be used.

[0075] The above-mentioned resist underlayer coating process can be omitted, and the following description will focus on the case where the resist underlayer is coated.

[0076] 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 a temperature of approximately 100°C to approximately 500°C, for example, at approximately 100°C to approximately 300°C.

[0077] The resist underlayer film 104 is formed between the substrate 100 and the photoresist film 106, and when irradiation lines reflected from the interface or interlayer hard mask between the substrate 100 and the photoresist film 106 are scattered into unintended photoresist regions, it can prevent non-uniformity of the photoresist linewidth and interference with pattern formation.

[0078] Referring to Figure 2(b), the aforementioned semiconductor photoresist composition is coated onto the resist underlayer film 104 to form a photoresist film 106. The photoresist film 106 may be formed by coating a thin film 102 formed on the substrate 100 with the aforementioned semiconductor photoresist composition and then curing it through a heat treatment process.

[0079] More specifically, the step of forming a pattern using a semiconductor photoresist composition may include the steps of applying the aforementioned 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.

[0080] Since the compositions for semiconductor photoresists have already been explained in detail, we will omit further explanation.

[0081] 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.

[0082] Referring to Figure 1(c), the photoresist film 106 is selectively exposed using a patterned mask 110.

[0083] As an example, examples of light that can be used in the exposure process include not only light such as the activation irradiation diagram i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), but also light with high energy wavelengths such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0084] More specifically, the exposure light in this embodiment may be light having a wavelength range of 5 nm to 150 nm, and may be light having a high energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0085] The exposed region 106b of the photoresist film 106 can have a different solubility from the unexposed region 106a of the photoresist film 106 by forming a polymer through crosslinking reactions such as condensation between organometallic compounds.

[0086] 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 less soluble in the developer.

[0087] Figure 1(d) shows the 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 and then removing the photoresist film 106a corresponding to the unexposed region using an organic solvent such as 2-heptanone.

[0088] As described above, the developer used in the pattern formation method of this embodiment may be an organic solvent. Examples of organic solvents used in the pattern formation method of this embodiment include ketones such as methyl ethyl ketone, acetone, cyclohexanone, and 2-haptanone; 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.

[0089] However, the photoresist pattern of this 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 tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or quaternary ammonium hydroxide compositions such as combinations thereof.

[0090] 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 UltraViolet; wavelength 13.5nm) and E-Beam (electron beam), can have a thickness width of 5nm to 100nm. For example, the photoresist pattern 108 may be formed with a thickness width of 5nm to 90nm, 5nm to 80nm, 5nm to 70nm, 5nm to 60nm, 5nm to 50nm, 5nm to 40nm, 5nm to 30nm, or 5nm to 20nm.

[0091] 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.

[0092] Next, the photoresist pattern 108 is used as an etching mask to etch the resist underlayer film 104. This etching process forms an organic film pattern 112. The formed organic film pattern 112 can have a width corresponding to the photoresist pattern 108.

[0093] 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 with the thin film pattern 114.

[0094] The thin film 102 can be etched, for example, by dry etching using an etching gas. The etching gas can be, for example, CHF3, CF4, Cl2, BCl3, or a mixture thereof.

[0095] In the aforementioned exposure process, the thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process using an EUV light source 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, or 5 nm to 20 nm, similar to the photoresist pattern 108, and more specifically, it may be formed with a width of 20 nm or less. [Examples]

[0096] The present invention will be described in more detail below through examples relating to the manufacture of the semiconductor photoresist composition mentioned above. However, the technical features of the present invention are not limited by the following examples.

[0097] Synthesis of organometallic compounds Synthesis Example 1 Add 0.7 g of t-ButylSnPh and 300 g of propionic acid to a 250 ml two-necked round-bottom flask and heat under reflux for 24 hours. Remove unreacted propionic acid under reduced pressure to obtain the compound represented by the following chemical formula 6. [ka]

[0098] Synthesis Example 2 Add 30 ml of anhydrous pentane to 10 g of t-AmylSnCl3, maintain the temperature at 0°C, then add 7.4 g of diethylamine and 6.1 g of ethanol, and stir at room temperature for 1 hour. Once the reaction is complete, filter, concentrate, and vacuum dry to obtain the compound represented by the following chemical formula 7. [ka]

[0099] 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, washed three times with 25 mL of deionized water, and then dried under reduced pressure at 100°C to obtain an organometallic compound represented by the following chemical formula 8 with a weight-average molecular weight of 1,500 g / mol. [ka]

[0100] (Manufacturing of semiconductor photoresist compositions) Examples and Comparative Examples Each of the organometallic compounds represented by chemical formulas 6 to 8 obtained from Synthesis Examples 1 to 3, along with the compounds of chemical formulas 1-1 to 1-3, 2-1 to 2-4, 9, and 10, were dissolved in Propylene glycol methyl ether acetate (PGMEA) at the concentrations shown in Table 1 below. The mixture was then filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to produce 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.

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] [Table 1]

[0105] Evaluation 1: Evaluation of sensitivity and LER A linear array of 50 circular pads with a diameter of 500 μm was projected onto a wafer coated with the semiconductor photoresist compositions described in the above examples and comparative examples using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). The pad exposure time was adjusted so that the increasing EUV dose was applied to each pad.

[0106] Subsequently, the resist and substrate were exposed on a hot plate at 160°C for 120 seconds, followed by post-exposure baking (PEB). The baked films were then immersed in a developer (2-heptanone) for 30 seconds each, and then washed with the same developer for an additional 10 seconds to form a negative tone image, i.e., to remove any unexposed coating areas. Finally, the process was completed by baking on a hot plate at 150°C for 2 minutes.

[0107] The residual resist thickness of the exposed pads was measured using a polarization analysis method (Ellipsometer). The remaining thickness was measured for each exposure level and graphed as a function of the exposure level. The Dg (energy level at which development is completed) was measured for each type of resist and is shown in Table 2 below.

[0108] The line edge roughness (LER) is measured from the line edge roughness (LER) of the formed pattern confirmed from the CD-SEM image, and is shown in Table 2 below.

[0109] [Table 2]

[0110] Referring to Table 2 above, it can be confirmed that the patterns formed using the semiconductor photoresist compositions of Examples 1 to 26 exhibit superior sensitivity and a smaller LER compared to Comparative Examples 1 to 10. This demonstrates that the semiconductor photoresist compositions of this embodiment have excellent sensitivity and pattern-forming properties.

[0111] Evaluation 2: Evaluation of storage stability The semiconductor photoresist compositions produced according to the aforementioned examples and comparative examples were stored in vials under room temperature and atmospheric pressure conditions, and the presence or absence of precipitate was visually checked for 5 days. X was used to indicate the presence of precipitate, and ○ to indicate the absence of precipitate. The results are shown in Table 3 below.

[0112] [Table 3]

[0113] Referring to Table 3 above, it was confirmed that the semiconductor photoresist composition according to the example showed no precipitate in the composition and no change in viscosity or turbidity even after 5 days. On the other hand, the photoresist composition according to the comparative example showed precipitate in the composition and a change in viscosity and turbidity after 5 days. This demonstrates that the semiconductor photoresist composition of this embodiment has excellent storage stability.

[0114] As described above, specific embodiments of the present invention have been explained and shown, but the present invention is not limited to the described embodiments, and it is obvious to those who are ordinarily skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention. Accordingly, such modifications or variations should not be understood individually from the technical spirit or viewpoint of the present invention, and the modified embodiments should fall within the scope of the claims of the present invention. [Explanation of Symbols]

[0115] 100...Substrate, 102...Thin film, 104...Resist underlayer film, 106...Photoresist film, 106a...Unexposed area, 106b...Exposed area, 108...Photoresist pattern, 112...Organic film pattern, 110...Patterned mask, 114...Thin film pattern.

Claims

1. organometallic compounds; Compound A, represented by the following chemical formula 1 or chemical formula 2; and Compositions for semiconductor photoresists containing a solvent: 【Chemistry 1】 In the aforementioned chemical formula 1, X １ and X ２ Each of these is independently a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C3 to C20 heteroaryl group, or a substituted or unsubstituted C6 to C20 aryl group, or the aforementioned X １ and X ２ These are connected to each other to form one or more rings: 【Chemistry 2】 In the aforementioned chemical formula 2, M １ is selected from -C(=O)-, -O-, -S-, -N(-L ｘ -R ｘ )-(where L ｘ is a single bond or a substituted or unsubstituted C1-C5 alkylene group, and R ｘ is hydrogen, a carboxyl group, or a substituted or unsubstituted C1-C5 alkyl group), or a combination thereof, L １ and L ２ Each of these is independently a single bonded, substituted, or unsubstituted C1 to C5 alkylene group. Z １ and Z ２ Each of these is independently a hydroxyl group, halogen, cyano group, cyano-containing group, ammonium group, amide group, nitro group, carboxyl group, ester group, sulfone group, sulfonate group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, or a combination thereof. n １ and n ２ Each of these is independently one of the integers from 0 to 4.

2. X of the aforementioned chemical formula 1 １ and X ２ Each of these is independently a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, and the X １ and X ２ The semiconductor photoresist composition according to claim 1, wherein at least one of the groups is a substituted or unsubstituted C6 to C20 aryl group.

3. X of the aforementioned chemical formula 1 １ and X ２ Each of these is independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, and the X １ and X ２ The semiconductor photoresist composition according to claim 1, wherein the elements are linked together to form one or more rings.

4. Z of the aforementioned chemical formula 2 １ and Z ２ The semiconductor photoresist composition according to claim 1, wherein each of them is independently a halogen, a carboxyl group, a sulfonate group, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C1 to C20 alkyl group.

5. The semiconductor photoresist composition according to claim 1, wherein the compound represented by the chemical formula 1 is one or more compounds selected from the following group 1: 【Transformation 3】

6. The semiconductor photoresist composition according to claim 1, wherein the compound represented by the chemical formula 2 is one or more compounds selected from the following group 2: 【Chemistry 4】

7. The semiconductor photoresist composition according to claim 1, wherein compound A represented by chemical formula 1 or chemical formula 2 is contained in an amount of 0.01% to 5% by weight based on 100% by weight of the semiconductor photoresist composition.

8. 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.

9. 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.

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

11. The organometallic compound is represented by the following chemical formula 3, and is the semiconductor photoresist composition according to claim 1: 【Transformation 5】 In the aforementioned chemical formula 3, R １ This is selected from substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C3 to C20 cycloalkyl groups, substituted or unsubstituted C2 to C20 alkenyl groups, substituted or unsubstituted C2 to C20 alkynyl groups, substituted or unsubstituted C6 to C30 aryl groups, and substituted or unsubstituted C7 to C30 arylalkyl groups. R ２ ~R ４ Each of these independently comprises 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 Here, R ｂ (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), a carboxyl group or an acyloxy group (-O(CO)R ｃ , R ｃ (-NR) 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), amidate (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), amidinate (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 ２ ~R ４ At least one of them is an alkoxy and an aryloxy (-OR ｂ Here, R ｂ (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), a carboxyl group or an acyloxy group (-O(CO)R ｃ , R ｃ (-NR) 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), amidate (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), amidinate (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 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, 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.)

12. The aforementioned R ２ ~R ４ 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 and acyloxy groups (-O(CO)R ｃ , R ｃ The semiconductor photoresist composition according to claim 11, wherein is selected from hydrogen, 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.

13. The aforementioned R １ These are selected from substituted or unsubstituted C1 to C8 alkyl groups, substituted or unsubstituted C3 to C8 cycloalkyl groups, substituted or unsubstituted C2 to C8 alkenyl groups, substituted or unsubstituted C2 to C8 alkynyl groups, substituted or unsubstituted C6 to C20 aryl groups, and substituted or unsubstituted C7 to C20 arylalkyl groups. 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 The semiconductor photoresist composition according to claim 12, wherein is hydrogen, 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.

14. The organometallic compound is represented by the following chemical formula 4 or the following chemical formula 5, and is part of the semiconductor photoresist composition according to claim 1: 【Transformation 6】 In the aforementioned chemical formula 4, R ５ These are the C1 to C31 hydrocarbyl groups, where 0 < z ≤ 2 and 0 < (z + x) ≤ 4; 【Transformation 7】 In the aforementioned chemical formula 5, R ６ 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.

15. The semiconductor photoresist composition according to claim 1, wherein the weight ratio of compound A to the organometallic compound (compound A: organometallic compound) is 0.02 or more and 0.10 or less.

16. The step of forming the film to be etched on the substrate; A step of forming a photoresist film by applying the semiconductor photoresist composition according to any one of claims 1 to 15 onto the film to be etched; The step of patterning the photoresist film to form a photoresist pattern; and, A pattern formation method comprising the step of etching a film to be etched using the aforementioned photoresist pattern as an etching mask.

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