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

Abstract

To provide a semiconductor photoresist composition that can achieve excellent sensitivity and excellent LER characteristics.SOLUTION: The present invention relates to a semiconductor photoresist composition including: a Sn-containing organometallic compound; a carboxylic acid compound; at least one compound selected from sulfonic acid compounds and phosphonic acid compounds; and a solvent, and a method of forming patterns using the semiconductor photoresist composition.SELECTED DRAWING: Figure 5

Description

[Technical Field]

[0001] This description relates to a semiconductor photoresist composition and a pattern formation method 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] The realization of extreme ultraviolet (EUV) lithography requires the development of compatible photoresists capable of 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 resulting from 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 photoresist at a wavelength of 13.5 nm, resulting in reduced sensitivity, and they may experience further difficulties, partly under EUV exposure.

[0005] CA photoresists also experience difficulties due to roughness issues at small feature sizes, and experiments have revealed that line edge roughness (LER) increases as the photospeed decreases, partly due to the nature of the acid-catalyzed process. Due to the shortcomings and problems of CA photoresists, the semiconductor industry has a demand for 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 that is resistant to removal by developer compositions through chemical modification via a non-chemical amplification mechanism. Inorganic compositions contain inorganic elements that have a higher EUV absorption rate compared to hydrocarbons, and are known to ensure sensitivity even with a non-chemical amplification mechanism, be less sensitive to the stochastic effect, and have fewer line edge roughness and defects.

[0007] Inorganic photoresists based on tungsten and peroxopolyacids of tungsten 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, being deep UV, X-ray, and electron beam sources, have been effective in patterning large features in bilayer configurations. More recently, impressive performance has been demonstrated when using cationic hafnium metal oxide sulfate (HfSOx) materials with a peroxo complexing agent to image a 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 superior performance for non-CA photoresists and possesses 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. First, these materials are coated with a highly corrosive sulfuric acid / hydrogen peroxide mixture, resulting in poor shelf-life stability. Second, structural modifications to improve performance are not easy as they are composite mixtures. Third, they must be developed with extremely high concentrations of TMAH (tetramethylammonium hydroxide) solution, such as 25 wt%.

[0009] Recently, with the discovery that tin-containing molecules exhibit outstanding extreme ultraviolet absorption, active research has been conducted. In the case of organotin polymers, one such example, negative tone patterning is possible, where alkyl ligands dissociate due to light absorption or the secondary electrons generated by it, and crosslinking via oxo bonds with surrounding chains prevents removal by organic developers. While such organotin polymers have shown a dramatic improvement in sensitivity while maintaining resolution and line edge roughness, 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 that exhibits excellent sensitivity and line edge roughness (LER) characteristics, and has improved sensitivity.

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

[0012] A semiconductor photoresist composition according to one embodiment comprises a Sn-containing organometallic compound; a carboxylic acid compound; at least one sulfonic acid compound and a phosphonic acid compound; and a solvent.

[0013] A pattern formation method according to another embodiment includes the steps of forming an etching target film on a substrate, forming a photoresist film by applying the aforementioned semiconductor photoresist composition on the etching target film, forming a photoresist pattern by patterning the photoresist film, and etching the etching target film using the photoresist pattern as an etching mask. [Effects of the Invention]

[0014] A semiconductor photoresist composition according to one embodiment enables excellent sensitivity and excellent LER characteristics. [Brief explanation of the drawing]

[0015] [Figure 1] This is a cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment. [Figure 2] This is a cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment. [Figure 3] This is a cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment. [Figure 4] This is a cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment. [Figure 5] 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]

[0016] The embodiments of the present invention will be described in detail below with reference to the attached drawings. However, in order to clarify the gist of this description, explanations of functions or configurations that are already known will be omitted.

[0017] To clearly explain this description, unnecessary explanatory parts have been omitted, and the same or similar components are denoted by the same reference numerals throughout the specification. 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.

[0018] In the drawings, the thicknesses were enlarged to clearly represent various layers and regions. Furthermore, for ease of explanation, the thicknesses of some layers and regions were exaggerated in the drawings. When a layer, film, region, plate, or other part is considered 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 there are other parts in between.

[0019] In this description, "substituted" means that the hydrogen atom is replaced by deuterium, a halogen group, a hydroxyl group, a carboxyl group, a thiol group, a cyano group, a nitro group, -NRR' (where 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'' (where R, R', and R'' are independently This means that the 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 is not substituted by another substituent and remains as a hydrogen atom.

[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-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.

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

[0023] The cycloalkyl group may be a C3-C8 cycloalkyl group, for example, a C3-C7 cycloalkyl group, a C3-C6 cycloalkyl group, a C3-C5 cycloalkyl group, or a C3-C4 cycloalkyl group. For example, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and is not limited to these.

[0024] In this specification, "aliphatic unsaturated organic group" means a hydrocarbon group in which the bonds between carbon atoms in the molecule are double bonds, triple bonds, or combinations thereof.

[0025] The aliphatic unsaturated organic group may be a C2-C8 aliphatic unsaturated organic group. For example, the aliphatic unsaturated organic group may be a C2-C7 aliphatic unsaturated organic group, a C2-C6 aliphatic unsaturated organic group, a C2-C5 aliphatic unsaturated organic group, or a C2-C4 aliphatic unsaturated organic group. For example, the C2-C4 aliphatic unsaturated organic group may be a vinyl group, an ethynyl group, an allyl group, a 1-propenyl group, a 1-methyl-1-propenyl group, a 2-propenyl group, a 2-methyl-2-propenyl group, a 1-propynyl group, a 1-methyl-1-propynyl group, a 2-propynyl group, a 2-methyl-2-propynyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group.

[0026] 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 fusion-ring polycyclic (i.e., rings that share adjacent pairs of carbon atoms) functional groups.

[0027] 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 by 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.

[0028] In this specification, "alkenyl group" means a linear or branched aliphatic hydrocarbon group containing one or more double bonds, which is an aliphatic unsaturated alkenyl group, unless otherwise defined.

[0029] In this specification, "alkynyl group" means a linear or branched aliphatic hydrocarbon group containing one or more triple bonds, which is an aliphatic unsaturated alkynyl group, unless otherwise defined.

[0030] A semiconductor photoresist composition according to one embodiment will be described below.

[0031] A semiconductor photoresist composition according to one embodiment of the present invention may contain at least one of a sn-containing organometallic compound, a carboxylic acid compound, a sulfonic acid compound, and a phosphonic acid compound, and a solvent.

[0032] The aforementioned semiconductor photoresist composition, by containing at least two acid compounds, namely a carboxylic acid compound and at least one sulfonic acid compound and a phosphonic acid compound, can improve sensitivity and LER and achieve excellent resolution.

[0033] As an example, the carboxylic acid compound, at least one of the sulfonic acid compound and phosphonic acid compound are included in a weight ratio of 1:0.001 to 1:10.

[0034] As a specific example, the carboxylic acid compound, at least one of the sulfonic acid compound and phosphonic acid compound are included in a weight ratio of 1:0.01 to 1:7.

[0035] The carboxylic acid compound is represented by the following chemical formula 1. [ka] In the above chemical formula 1, R 1 These are amine groups, halogens, hydroxyl groups, carboxyl groups, 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 substituted or unsubstituted C7-C30 arylalkyl groups. L 1 and L 2 Each of these is independently a single bond, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C6-C30 arylene group, or a combination thereof. X 1 These are single bonds, O, S, or NR 2 (R 2is 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 m1 is an integer of 1 or more.

[0036] The upper limit value of m1 may be the maximum value that can be linked to L 2 but m1 may be within a range below the maximum value, for example, in the range of 1 to 10, 1 to 8, 1 to 6, or 1 to 3.

[0037] The sulfonic acid compound is represented by the following chemical formula 2. [Chemical formula] In the chemical formula 2, R 3 is an amine group, a halogen, a hydroxy group, a carboxyl group, 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 substituted or unsubstituted C7-C30 arylalkyl group, and L 3 and L 4 are each independently a single bond, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C6-C30 arylene group, or a combination thereof, X 2 is a single bond, O, S or NR 4 (R 4 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), and m2 is an integer of 1 or more.

[0038] The upper limit of m2 is L 4 m2 may be the maximum value that can be connected to it, but m2 may also be within a range less than or equal to the above maximum value, for example, in the range of 1 to 10, 1 to 8, 1 to 6, or 1 to 3.

[0039] The phosphonic acid compound is represented by the following chemical formula 3. [ka] In the aforementioned chemical formula 3, R 5 These are amine groups, halogens, hydroxyl groups, carboxyl groups, 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 substituted or unsubstituted C7-C30 arylalkyl groups. L 5 and L 6 Each of these is independently a single bond, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C6-C30 arylene group, or a combination thereof. X 3 These are single bonds, O, S, or NR 6 (R 6 (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.) m3 is an integer greater than or equal to 1.

[0040] The upper limit of m3 is L 6 m3 may be the maximum value that can be connected, but it may also be within a range less than or equal to the above maximum value, for example, in the range of 1 to 10, 1 to 8, 1 to 6, or 1 to 3.

[0041] For example, the R1 , R 3 and R 5 Each of these may independently be a hydroxyl group, a carboxyl group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted iso-propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted iso-butyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted benzyl group.

[0042] For example, L 1 ~L 6 Each of these may independently be a single bond, a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, a substituted or unsubstituted pentylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group.

[0043] As a specific example, the carboxylic acid compound may be one of the compounds listed in Group 1 below. [ka]

[0044] As a specific example, the sulfonic acid compound and the phosphonic acid compound may be one of the compounds listed in Group 2 below. [ka]

[0045] The carboxylic acid compound and at least one of the sulfonic acid compound and phosphonic acid compound are present in a total amount of 0.001 to 10% by weight per 100% by weight of the semiconductor photoresist composition.

[0046] For example, the carboxylic acid compound and at least one of the sulfonic acid compound and phosphonic acid compound are included in total at 0.01 to 10% by weight, 0.01 to 5% by weight, 0.05 to 5% by weight, or 0.1 to 5% by weight, based on 100% by weight of the semiconductor photoresist composition.

[0047] The aforementioned Sn-containing organometallic compound is present in an amount of 0.5% to 30% by weight relative to 100% by weight of the semiconductor photoresist composition.

[0048] A semiconductor photoresist composition according to one embodiment can improve the sensitivity of a photoresist by containing the Sn-containing organometallic compound, the carboxylic acid compound, and at least one of the sulfonic acid compound and phosphonic acid compound in the aforementioned content range.

[0049] A semiconductor photoresist composition according to one embodiment may contain the Sn-containing organometallic compound:at least one of the carboxylic acid compound, the sulfonic acid compound, and the phosphonic acid compound in a weight ratio of 99:1 to 80:20. For example, a semiconductor photoresist composition may contain the Sn-containing organometallic compound:at least one of the carboxylic acid compound, the sulfonic acid compound, and the phosphonic acid compound in a weight ratio of 99:1 to 90:10.

[0050] When the weight ratio of the Sn-containing organometallic compound to the acid compound satisfies the aforementioned range, a semiconductor photoresist composition with excellent sensitivity can be provided.

[0051] The Sn-containing organometallic compound may contain at least one of an organic oxy group and an organic carbonyl oxy group.

[0052] The aforementioned organometallic compound is represented by the following chemical formula 4. [ka] In the aforementioned chemical formula 4, R7 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 C6-C30 arylalkyl groups. R 8 ~R 10 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 C6-C30 arylalkyl groups, alkoxo and aryloxo (-OR a , 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), carboxyl groups (-O(CO)R b , R b (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 c R d , here, R c and R d 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 e (COR f), here, R e and R f 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 g , R h and R i 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 j , here, R j (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 k , R k (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 8 ~R 10 At least one of them is an alcoxo and an aryl oxo (-OR a , 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), carboxyl groups (-O(CO)R b , R b (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 c R d , here, R c and R d 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 e (COR f ), here, R e and R f 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 g , R h and R iEach 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 j , here, R j (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 k , R k (The group 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.)

[0053] The aforementioned R 8 ~R 10 At least one of them is an alcoxo and an aryl oxo (-OR a , 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 b , R b (The group 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.)

[0054] On the other hand, the compound represented by chemical formula 4 has -OR as a ligand. a Or -OC(=O)R b By including this, patterns formed using a semiconductor photoresist composition containing it can exhibit excellent limiting resolution.

[0055] Also, -OR a Or -OC(=O)R b The ligand can determine the solubility of the compound represented by chemical formula 4 in a solvent.

[0056] The aforementioned R 7 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 a 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 b 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.

[0057] The aforementioned R 7is a 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, propynyl group, butynyl group, phenyl group, tolyl group, xylyl group, benzyl group, formyl group, acetyl group, propanoyl group, butanoyl group, pentanoyl group, ethoxy group, propoxy group, or a combination thereof, R a is an 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, propynyl group, butynyl group, phenyl group, tolyl group, xylyl group, benzyl group, or a combination thereof, R b is hydrogen, an 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, propynyl group, butynyl group, phenyl group, tolyl group, xylyl group, benzyl group, or a combination thereof.

[0058] Further, the Sn-containing organometallic compound is represented by the following Chemical Formula 5 or Chemical Formula 6.

Chemical formula

Chemical formula

[0059] 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.

[0060] The semiconductor resist composition according to one embodiment may further contain a resin in addition to the Sn-containing organometallic compound, acid compound, and solvent.

[0061] The aforementioned resin may be a phenolic resin containing at least one aromatic molecule listed in Group 3 below. [ka] The resin may have a weight-average molecular weight of 500 to 20,000.

[0062] The resin is present in an amount of 0.1% to 50% by weight relative to the total content of the semiconductor photoresist composition.

[0063] When the aforementioned resin is included within the aforementioned content range, it can have excellent etching resistance and heat resistance.

[0064] On the other hand, the semiconductor photoresist composition is preferably composed of the aforementioned Sn-containing organometallic compound, acid compound, solvent, and resin.

[0065] The semiconductor photoresist compositions according to the embodiments described above may optionally further contain additives. Examples of such additives include surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0066] The surfactant may be, but is not limited to, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts, or combinations thereof.

[0067] 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-cyclohexane dicarboxylate, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea.

[0068] Leveling agents are used to improve the flatness of the coating during printing, and commercially available, known leveling agents can be used.

[0069] 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.

[0070] The quencher may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0071] The amount of these additives used can be easily adjusted according to the desired physical properties, and may even be omitted.

[0072] Furthermore, the semiconductor photoresist composition may further use 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.

[0073] 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 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 the 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.

[0074] On the other hand, according to other embodiments, 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.

[0075] A pattern formation method according to one embodiment includes the steps of forming an etching target film on a substrate, forming a photoresist film by applying the aforementioned semiconductor photoresist composition on the etching target film, forming a photoresist pattern by patterning the photoresist film, and etching the etching target film using the photoresist pattern as an etching mask.

[0076] The method for forming a pattern using the semiconductor photoresist composition described above will be explained below with reference to Figures 1 to 5. Figures 1 to 5 are cross-sectional views illustrating the pattern formation method using the semiconductor photoresist composition according to the present invention.

[0077] Referring to Figure 1, 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.

[0078] 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, and printing methods, such as inkjet printing and screen printing, may also be used.

[0079] The coating process for the resist underlayer can be omitted, and the following describes the case where the resist underlayer is coated.

[0080] 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.

[0081] The resist underlayer 104 is formed between the substrate 100 and the photoresist film 106, and when irradiation lines reflected from the interface between the substrate 100 and the photoresist film 106 or from the interlayer hard mask scatter into unintended photoresist regions, it can prevent non-uniformity of the photoresist linewidth and interference with pattern formation.

[0082] Referring to Figure 2, the aforementioned 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 a thin film 102 formed on the substrate 100 with the aforementioned semiconductor photoresist composition and then curing it through a heat treatment process.

[0083] More specifically, the step of forming a pattern using a semiconductor photoresist composition may include the steps of applying the above-mentioned 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.

[0084] Since the compositions for semiconductor photoresists have already been explained in detail, we will omit further explanation.

[0085] 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.

[0086] Referring to Figure 3, the photoresist film 106 is selectively exposed using a patterned mask 110.

[0087] As an example, examples of light that can be used in the exposure process include not only short-wavelength 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 high-energy wavelength light such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0088] More specifically, the exposure light in one embodiment may be short-wavelength 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 UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0089] The exposed region 106a in the photoresist film 106 has a different solubility from the unexposed region 106b of the photoresist film 106, due to the formation of polymers through crosslinking reactions such as condensation between organometallic compounds.

[0090] Next, a second baking step is performed on the substrate 100. The second baking step can be performed at a temperature of approximately 90°C to approximately 200°C. By performing the second baking step, the exposed region 106a of the photoresist film 106 becomes less soluble in the developer.

[0091] Figure 4 shows the photoresist pattern 108 formed by dissolving and removing the photoresist film 106b 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 106b corresponding to the unexposed region using an organic solvent such as 2-heptanone, and then removing it.

[0092] As explained earlier, the developer used in the pattern formation method according to one embodiment may be an organic solvent. Examples of organic solvents used in the pattern formation 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.

[0093] However, the photoresist pattern according to one embodiment is not necessarily limited to the formation of a negative tone image, but may be formed to have a positive tone image. In this case, examples of developers that can be used for forming a positive tone image include quaternary ammonium hydroxide compositions such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof.

[0094] As explained earlier, 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 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.

[0095] 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.

[0096] 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 may also have a width corresponding to the photoresist pattern 108.

[0097] Referring to Figure 5, 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 on the thin film pattern 114.

[0098] 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.

[0099] 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, the same as 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]

[0100] The present invention will be described in more detail below through the examples of the manufacturing of the semiconductor photoresist composition described above. However, the technical features of the present invention are not limited by the following examples.

[0101] Synthesis of organometallic compounds Synthesis Example 1 Place 340.7g of t-butylSnPh and 300g of propionic acid in a 250ml two-necked round-bottom flask and heat under reflux for 24 hours.

[0102] The unreacted propionic acid is removed under reduced pressure to obtain the compound represented by the following chemical formula 7. [ka]

[0103] Synthesis Example 2 Dissolve 318.9g of iPrSn(NEt2) in 500mL of anhydrous hexane in a 1L round-bottom flask. After cooling the flask to -78°C, slowly add 9.0g of iPrOH dropwise, and allow to react at room temperature for 24 hours. Once the reaction is complete, concentrate the mixture and vacuum dry it to obtain the compound represented by the following chemical formula 8. [ka]

[0104] 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 with a weight-average molecular weight of 1,500 represented by the following chemical formula 9. [ka]

[0105] Manufacturing of semiconductor photoresist compositions Examples 1-9 and Comparative Examples 1-3 The organometallic compounds represented by chemical formulas 7 to 9 obtained in Synthesis Examples 1 to 3, along with carboxylic acid compounds and phosphonic acid compounds, are dissolved in Propylene glycol methyl ether acetate (PGMEA) at a concentration of 3 wt% in the weight ratios shown in Table 1 below. The mixture is then filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to produce a semiconductor photoresist composition.

[0106] [Table 1]

[0107] C1: Propionic acid P1: 3-Phosphonopropanoic acid S1:3-Hydroxypropane-1-sulfonic acid

[0108] Evaluation 1: Sensitivity and Line Edge Roughness (LER) Evaluation On a 200 mm circular silicon wafer whose surface is coated with HMDS, the photoresist compositions according to the above examples and comparative examples are spin-coated 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.

[0109] 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.

[0110] Subsequently, the resist and substrate were placed on a hot plate and exposed at 160°C for 120 seconds, followed by firing. The fired film was developed with PGMEA solvent to form a negative tone image. Finally, the process was completed by hot plate firing at 150°C for 2 minutes.

[0111] The thickness of the residual resist on 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 LER was measured from the FE-SEM image. After that, sensitivity and line edge roughness were evaluated according to the following criteria, and the results are shown in Table 2.

[0112] [Sensitivity evaluation criteria] -A: 16mJ / cm 2 less than -B: 16mJ / cm 2 That's all.

[0113] [LER Evaluation Criteria] -○: 2nm or less -△: More than 2nm and less than 5nm -X: Exceeding 5nm

[0114] Rating 2: Resolution (CD) Rating After the process was completed, the pattern wafer had a Line / Space CD pattern formed on it. Subsequently, it was transferred to a CD-SEM measuring device (GC-9380, Hitachi) to measure the CD (Critical Dimension) size at the half-pitch of the mask pattern at 14 nm. The minimum value of the space CD, which is the distance between lines, is shown in Table 2.

[0115] [Table 2]

[0116] The results in Table 2 confirm that the patterns formed using the semiconductor photoresist compositions of Examples 1-9 exhibit superior sensitivity, LER, and resolution characteristics compared to Comparative Examples 1-3.

[0117] Although specific embodiments of the present invention have been described and illustrated above, it will be 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. Accordingly, such modifications or variations should not be understood individually from the technical spirit or viewpoint of the present invention, and the modified embodiments fall within the scope of the claims of the present invention. [Explanation of Symbols]

[0118] 100...Substrate, 102...Thin film, 104...Resist underlayer film, 106...Photoresist film, 106a...Exposed region, 106b...Unexposed region, 108...Photoresist pattern, 112...Organic film pattern, 110...Patterned mask, 114...Thin film pattern.

Claims

1. Sn-containing organometallic compound; Carboxylic acid compounds; At least one sulfonic acid compound and a phosphonic acid compound; and solvent Includes, The aforementioned sulfonic acid compound is represented by the following chemical formula 2: 【Chemistry 1】 In the aforementioned chemical formula 2, R3 is an amine group, halogen, hydroxyl group, carboxyl group, substituted or unsubstituted C1-C20 alkyl group, substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C2-C20 alkenyl group, substituted or unsubstituted C2-C20 alkynyl group, substituted or unsubstituted C6-C30 aryl group, or substituted or unsubstituted C7-C30 arylalkyl group. L3 and L4 are, independently, single bonds, substituted or unsubstituted C1-C20 alkylene groups, substituted or unsubstituted C6-C30 arylene groups, or combinations thereof. X2 is a single bond, O, S, or NR4 (R4 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). m2 is an integer greater than or equal to 1. A composition for semiconductor photoresists.

2. The semiconductor photoresist composition according to claim 1, wherein the carboxylic acid compound: at least one of the sulfonic acid compound and the phosphonic acid compound is contained in a weight ratio of 1:0.001 to 1:

10.

3. The semiconductor photoresist composition according to claim 1, wherein the carboxylic acid compound is represented by the following chemical formula 1: 【Chemistry 2】 In the aforementioned chemical formula 1, R 1 These are amine groups, halogens, hydroxyl groups, carboxyl groups, 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 substituted or unsubstituted C7-C30 arylalkyl groups. L 1 and L 2 Each of these is independently a single bond, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C6-C30 arylene group, or a combination thereof. X 1 is a single bond, O, S or NR 2 (R 2 (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.) m1 is an integer greater than or equal to 1.

4. The semiconductor photoresist composition according to claim 1, wherein the phosphonic acid compound is represented by the following chemical formula 3: 【Transformation 3】 In the aforementioned chemical formula 3, R 5 These are amine groups, halogens, hydroxyl groups, carboxyl groups, 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 substituted or unsubstituted C7-C30 arylalkyl groups. L 5 and L 6 are each independently a single bond, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C6-C30 arylene group, or a combination thereof, X 3 is a single bond, O, S or NR 6 (R 6 (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.) m3 is an integer greater than or equal to 1.

5. The semiconductor photoresist composition according to claim 1, wherein the carboxylic acid compound is at least one selected from the compounds listed in Group 1 below: 【Chemistry 4】 。

6. The semiconductor photoresist composition according to claim 1, wherein the sulfonic acid compound and the phosphonic acid compound are at least one selected from the compounds listed in Group 2 below: 【Transformation 5】 。

7. The semiconductor photoresist composition according to claim 1, wherein the carboxylic acid compound and at least one of the sulfonic acid compound and phosphonic acid compound are present in a total amount of 0.001 to 10% by weight per 100% by weight of the semiconductor photoresist composition.

8. The semiconductor photoresist composition according to claim 1, wherein the carboxylic acid compound and at least one of the sulfonic acid compound and phosphonic acid compound are present in a total amount of 0.1 to 5% by weight based on 100% by weight of the semiconductor photoresist composition.

9. The semiconductor photoresist composition according to claim 1, wherein the Sn-containing organometallic compound is present in an amount of 0.5% to 30% by weight based on 100% by weight of the semiconductor photoresist composition.

10. 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.

11. The semiconductor photoresist composition according to claim 1, wherein the Sn-containing organometallic compound comprises at least one of an organic oxy group and an organic carbonyl oxy group.

12. The Sn-containing organometallic compound is represented by the following chemical formula 4, and is the semiconductor photoresist composition according to claim 1: 【Transformation 6】 In the aforementioned chemical formula 4, R 7 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 C6-C30 arylalkyl groups. R 8 ~R 10 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 C6-C30 arylalkyl groups, alkoxo and aryloxo (-OR a Here, R a (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 b , R b (-NR) c R d Here, R c and R d 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 e (COR f ), here, R e and R f 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 g , R h and R i 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 j Here, R j (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 k , R k (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 8 ~R 10 At least one of them is an alcoxo and an aryl oxo (-OR a Here, R a (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 b , R b (-NR) c R d Here, R c and R d 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 e (COR f ), here, R e and R f 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 g , R h and R i 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 j Here, R j (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 k , R k (The group 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.)

13. The aforementioned R 8 ~R 10 At least one of them is an alcoxo and an aryl oxo (-OR a 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 b , R b The semiconductor photoresist composition according to claim 12, 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.

14. The aforementioned R 7 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 a 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 b The semiconductor photoresist composition according to claim 12, 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.

15. The Sn-containing organometallic compound is represented by the following chemical formula 5 or chemical formula 6, the semiconductor photoresist composition according to claim 1: 【Transformation 7】 In the aforementioned chemical formula 5, R 11 These are the C1-C31 hydrocarbyl group, where 0 < z ≤ 2 and 0 < (z + x) ≤ 4; 【Transformation 8】 In the aforementioned chemical formula 6, R 12 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 l or -OC(=O)R m And, The aforementioned R l 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 m 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. a1, b1, c1, and d1 are each independent integers between 1 and 20.

16. The steps include forming an etching target film on a substrate, The steps include applying the semiconductor photoresist composition described in any one of claims 1 to 15 to the etchable film to form a photoresist film, The steps include: patterning the aforementioned photoresist film to form a photoresist pattern; 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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