Semiconductor photoresist composition and pattern forming method using the same

Abstract

To provide a semiconductor photoresist composition excellent in sensitivity, line edge roughness (LER), and resolution characteristics, and to provide a pattern forming method using the same.SOLUTION: The present invention relates to: a semiconductor photoresist composition which contains an Sn-containing organometallic compound, a carboxylic acid compound containing at least one aryl group and an unsaturated bond, and a solvent; and a pattern forming method using the semiconductor photoresist composition.SELECTED DRAWING: Figure 1

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 elemental technologies for manufacturing next-generation semiconductor devices. EUV lithography is a pattern formation technology 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 (e.g., 20 nm or less) during the exposure process in semiconductor device manufacturing.

[0003] The realization of extreme ultraviolet (EUV) lithography requires the development of compatible photoresists capable of achieving spatial resolutions of 16 nm or less. Currently, traditional chemically amplified (CA) photoresists struggle to meet the specifications for resolution, photo speed, feature roughness, and line edge roughness (LER) for next-generation devices.

[0004] Intrinsic image blur due to acid-catalyzed reactions occurring in these polymeric photoresists limits resolution at small feature sizes, a problem long known in electron beam (e-beam) lithography. Chemically amplified (CA) photoresists, designed for high sensitivity, can be more challenging under EUV exposure, in part because their typical elemental makeup reduces the photoresist's absorbance at 13.5 nm wavelengths, thereby reducing sensitivity.

[0005] CA photoresists can suffer from roughness issues at small feature sizes, and experiments have shown that line edge roughness (LER) increases as the photospeed decreases, due in part to the nature of the acid-catalyzed process. Due to the shortcomings and problems of CA photoresists, the semiconductor industry is seeking new types of high-performance photoresists.

[0006] To overcome the drawbacks of the chemically amplified organic photosensitive compositions described above, inorganic photosensitive compositions have been developed. Inorganic photosensitive compositions are primarily used in negative-tone patterning, where they are chemically modified through a non-chemically amplified mechanism, making them resistant to removal by developer compositions. Inorganic compositions contain inorganic elements with higher EUV absorption than hydrocarbons, ensuring sensitivity even with a non-chemically amplified mechanism. They are also said to be less susceptible to the stochastic effect, resulting in fewer line edge roughness and fewer defects.

[0007] Inorganic photoresists based on peroxopolyacids of tungsten and tungsten mixed with niobium, titanium, and / or tantalum have been reported for patterning radiation-sensitive materials (US Pat. No. 5,061,599; H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298-300, 1986).

[0008] These materials have been effective in patterning large features in bilayer configurations with 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 peroxocomplexing agents to image 15 nm half-pitch (HP) patterns with projection EUV exposure (US 2011-0045406; J.K. Stowers, A. Telecky, M. Kocsis, B.L. Clark, D.A. Keszler, A. Grenville, C.N. Anderson, P.P. Naulleau, Proc. SPIE, 7969, 796915, 2011). This system exhibits the best performance of any non-CA photoresist and has a photospeed approaching the requirements for a viable EUV photoresist. However, hafnium metal oxide sulfate materials with 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, as a complex mixture, it is difficult to modify the structure to improve performance. Third, they must be developed using an extremely high concentration solution, such as 25 wt% TMAH (tetramethylammonium hydroxide).

[0009] In recent years, tin-containing molecules have been recognized as having excellent extreme UV absorption, and active research has been conducted on them. In the case of organotin polymers, one such polymer, alkyl ligands are dissociated by light absorption or the secondary electrons generated by the absorption, and crosslinking with surrounding chains via oxo bonds enables negative-tone patterning that is resistant to removal by organic developers. These organotin polymers have demonstrated dramatic improvements in sensitivity while maintaining resolution and line edge roughness. However, further improvements in their patterning properties are required for commercialization. Summary of the Invention [Problem to be solved by the invention]

[0010] An embodiment provides a composition for semiconductor photoresist having excellent sensitivity, line edge roughness (LER) and resolution characteristics.

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

[0012] A composition for semiconductor photoresist according to one embodiment includes a Sn-containing organometallic compound, a carboxylic acid compound having at least one aryl group and an unsaturated bond; and a solvent.

[0013] A pattern forming method according to another embodiment includes the steps of forming a layer to be etched on a substrate, applying the semiconductor photoresist composition described above on the layer to be etched to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and etching the layer to be etched using the photoresist pattern as an etching mask.

[0014] The semiconductor photoresist composition according to an embodiment can achieve excellent sensitivity and excellent LER characteristics. [Brief explanation of the drawings]

[0015] [Figure 1] 1A to 1C are cross-sectional views illustrating a method for forming a pattern using a semiconductor photoresist composition according to an embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0016] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings, but in this description, descriptions of known functions or configurations will be omitted in order to clarify the gist of the description.

[0017] In order to clarify the present description, parts not relevant to the description will be omitted, and the same or similar components will be designated by the same reference numerals throughout the specification. Furthermore, the size and thickness of each component shown in the drawings are arbitrarily shown for the convenience of explanation, and the present description is not necessarily limited to those shown.

[0018] In the drawings, thicknesses of multiple layers and regions are exaggerated to clearly show them. Also, in the drawings, thicknesses of some layers and regions are exaggerated for ease of explanation. When a layer, film, region, plate, or other portion is "on" or "above" another portion, this includes not only when it is "directly on" the other portion, but also when there is another portion between them.

[0019] In this description, "substituted" means that a hydrogen atom is replaced with a deuterium atom, a halogen group, a hydroxy group, a carboxyl group, a thiol group, a cyano group, a nitro group, -NRR' (wherein R and R' are each independently hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), -SiRR'R" (wherein R, R', and R" are each independently "Unsubstituted" means 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 with another substituent and remains a hydrogen atom.

[0020] As used herein, unless otherwise defined, the term "alkyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not have 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, a tert-butyl group, or a 2,2-dimethylpropyl group.

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

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

[0024] As used herein, the term "aliphatically unsaturated organic group" refers to a hydrocarbon group in which the bonds between carbon atoms in the molecule contain double bonds, triple bonds, or combinations thereof.

[0025] The aliphatic unsaturated organic group may be a C2 to C8 aliphatic unsaturated organic group. For example, the aliphatic unsaturated organic group may be a C2 to C7 aliphatic unsaturated organic group, a C2 to C6 aliphatic unsaturated organic group, a C2 to C5 aliphatic unsaturated organic group, or a C2 to C4 aliphatic unsaturated organic group. For example, the C2 to C4 aliphatic unsaturated organic group may be a vinyl group, an ethynyl group, an aryl group, a 1-propenyl group, a 1-methyl-1-propenyl group, a 2-propenyl group, a 2-methyl-2-propenyl group, a 1-propanyl group, a 1-methyl-1propanyl group, a 2-propanyl group, a 2-methyl-2-propanyl 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] As used herein, the term "aryl group" refers to a cyclic substituent in which all elements have p-orbitals and these p-orbitals form conjugation, and includes monocyclic or fused-ring polycyclic (i.e., rings that share adjacent pairs of carbon atoms) functional groups.

[0027] As used herein, the term "heteroaryl group" refers to 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 a sigma bond, or when the heteroaryl group contains two or more rings, the two or more rings may be fused to each other. When the heteroaryl group is a fused ring, each ring may contain 1 to 3 heteroatoms.

[0028] As used herein, unless otherwise defined, the term "alkenyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group that is an aliphatic unsaturated alkenyl group containing one or more double bonds.

[0029] As used herein, unless otherwise defined, the term "alkynyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group, an aliphatic unsaturated alkynyl group containing one or more triple bonds.

[0030] Hereinafter, a semiconductor photoresist composition according to an embodiment will be described.

[0031] A composition for semiconductor photoresist according to an embodiment of the present invention may include a Sn-containing organometallic compound, a carboxylic acid compound having at least one aryl group and unsaturated bond, and a solvent.

[0032] For example, the carboxylic acid compound may be a compound represented by the following Chemical Formula 1 or 2: [ka] In the above Chemical Formula 1, R 1 ~R 3 are each independently a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R 1 ~R 3 at least one of the groups is a substituted or unsubstituted C6 to C30 aryl group; L 1 is a single bond or a substituted or unsubstituted C1-C10 alkylene group; [ka] In the above Chemical Formula 2, R 4 is a substituted or unsubstituted C6 to C30 aryl group, L 2 is a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

[0033] The semiconductor photoresist composition can improve sensitivity and LER and achieve excellent resolution by using a carboxylic acid compound containing both an aryl group and an unsaturated bond.

[0034] For example, R in Formula 1 1 and R 2 At least one of the above or the R 3 may each independently be a substituted or unsubstituted C6 to C30 aryl group.

[0035] As a specific example, R 1 and R 2 At least one of the above or R 3 and R in Chemical Formula 2 4 may each independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, or a substituted or unsubstituted triphenylene group.

[0036] For example, the carboxylic acid compound may be one selected from the compounds listed in Group 1 below. [ka] The carboxylic acid compound can be contained in an amount of 0.001 to 10% by weight relative to 100% by weight of the semiconductor photoresist composition.

[0037] For example, the carboxylic acid compound can be contained in an amount of 0.01 to 10 wt %, 0.01 to 5 wt %, 0.05 to 5 wt %, or 0.1 to 5 wt % relative to 100 wt % of the semiconductor photoresist composition.

[0038] The Sn-containing organometallic compound may be contained in an amount of 0.5 to 30% by weight relative to 100% by weight of the composition for semiconductor photoresists.

[0039] The composition for semiconductor photoresist according to an embodiment contains the Sn-containing organometallic compound and the carboxylic acid compound in the above content ranges, thereby improving the sensitivity of the photoresist.

[0040] According to an embodiment, the semiconductor photoresist composition may contain the Sn-containing organometallic compound and the carboxylic acid compound in a weight ratio of 99:1 to 70:30. For example, the semiconductor photoresist composition may contain the Sn-containing organometallic compound and the carboxylic acid compound in a weight ratio of 99:1 to 80:20.

[0041] When the weight ratio of the Sn-containing organometallic compound to the carboxylic acid compound satisfies the above range, a semiconductor photoresist composition having excellent sensitivity can be provided.

[0042] The Sn-containing organometallic compound may include at least one of an organic oxy group and an organic carbonyloxy group.

[0043] The organometallic compound is represented by the following chemical formula 3. [ka] In the above Chemical Formula 3, R 9is selected from 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, and a substituted or unsubstituted C7 to C30 arylalkyl group; R 10 ~R 12 are each independently 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, a substituted or unsubstituted C7 to C30 arylalkyl group, alkoxy, and aryloxy (-OR a , where R a is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), a carboxyl group (-O(C=O)R b , R b is 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), alkylamide or dialkylamide (-NR c R d , where R c and R d are each independently 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), amidato (-NR e (C=OR f ), where R e and R fare each independently 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), amidinato (-NR g C(NR h )R i , where R g , R h and R i are each independently 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), alkylthio and arylthio (-SR j , where R j is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof) or a thiocarboxyl group (-SCO)R k , R k is 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; R 10 ~R 12 At least one of the groups is alkoxy and aryloxy (-OR a , where R ais 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), a carboxyl group (-O(C=O)R b , R b is 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), alkylamide or dialkylamide (-NR c R d , where R c and R d are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, an 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), amidato (-NR e (C=OR f ), where R e and R f are each independently 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), amidinato (-NR g C(NR h )R i , where R g , R h and R iare each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 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), alkylthio and arylthio (-SR j , where R j is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof) and a thiocarboxyl group (-S(C=O)R k , R k 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.

[0044] R 10 ~R 12 At least one of the groups is alkoxy and aryloxy (-OR a , where R a is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), and a carboxyl group (-O(C=O)R b , R b 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.

[0045] Meanwhile, the compound represented by the formula 3 has -OR as a ligand. a or -OC(=O)R b By including the compound (I), a pattern formed using a semiconductor photoresist composition containing the compound can exhibit excellent limit resolution.

[0046] Also, -OR a or -OC(=O)R b The ligand can determine the solubility of the compound represented by Chemical Formula 3 in a solvent.

[0047] R 9 is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group containing one or more double or triple bonds, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C4 to C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof; R a is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof; R b may be 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.

[0048] R 9is a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propenyl group, a butenyl group, an ethynyl group, a propynyl group, a butynyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pentanoyl group, an ethoxy group, a propoxy group, or a combination thereof; R a is an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propenyl group, a butenyl group, an ethynyl group, a propynyl group, a butynyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, or a combination thereof; R b may be hydrogen, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylene, benzyl, or a combination thereof.

[0049] The Sn-containing organometallic compound is represented by the following chemical formula 4 or 5. [ka] In the above Chemical Formula 4, R 13 is a C1 to C31 hydrocarbyl group, where 0 <z≦2であり、0<(z+x)≦4であり; [ka] In the above Chemical Formula 5, R 14is 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 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof; X is sulfur (S), selenium (Se), or tellurium (Te); Y is -OR l or -OC(=O)R m and R l is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R m is 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; The a1, b1, c1 and d1 are each independently an integer of 1 to 20.

[0050] The solvent contained in the semiconductor photoresist composition according to an embodiment may be an organic solvent, and examples thereof may include, but are 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.

[0051] The semiconductor resist composition according to an embodiment may further include a resin in addition to the Sn-containing organometallic compound, the acid compound, and the solvent.

[0052] The resin may be a phenolic resin containing at least one aromatic moiety listed in Group 2 below. [ka] The resin may have a weight average molecular weight of 500 to 20,000.

[0053] The resin may be contained in an amount of 0.1% by weight to 50% by weight based on the total content of the semiconductor photoresist composition.

[0054] When the resin is contained in the above content range, excellent etching resistance and heat resistance can be obtained.

[0055] On the other hand, the semiconductor photoresist composition preferably comprises the Sn-containing organometallic compound, an acid compound, a solvent, and a resin.

[0056] The semiconductor photoresist composition according to the above-described embodiment may further include an additive, if desired.

[0057] Examples of such additives include surfactants, crosslinkers, leveling agents, organic acids, quenchers, or combinations thereof.

[0058] The surfactant may be, for example, but not limited to, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, or a combination thereof.

[0059] Examples of the crosslinking agent include, but are not limited to, melamine-based crosslinking agents, substituted urea-based crosslinking agents, acrylic-based crosslinking agents, epoxy-based crosslinking agents, and polymer-based crosslinking agents. Examples of the crosslinking agent having at least two crosslink-forming substituents include methoxymethylated glycolyl, butoxymethylated glycolyl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, acrylic methacrylate, 1,4-butanediol diglycidyl ether, glycidol, diglycidyl 1,2-cyclohexanedicarboxylate, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, and methoxymethylated thiourea.

[0060] The leveling agent is used to improve the coating flatness during printing, and any known leveling agent that is commercially available can be used.

[0061] 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 sulfonates, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or combinations thereof.

[0062] The quencher may be diphenyl(p-toluyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0063] The amount of these additives used can be easily adjusted depending on the desired physical properties, and they may be omitted.

[0064] The semiconductor photoresist composition may further contain a silane coupling agent as an additive to enhance adhesion to a substrate (e.g., to improve the adhesive strength of the semiconductor photoresist composition to a substrate). Examples of the silane coupling agent include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; silane compounds containing a carbon-carbon unsaturated bond, such as 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; and trimethoxy[3-(phenylamino)propyl]silane.

[0065] The semiconductor photoresist composition may not cause pattern collapse even when forming a pattern having a high aspect ratio. Therefore, to form a fine pattern having a width of, for example, 5 nm to 100 nm, for example, a fine pattern having a width of 5 nm to 80 nm, for example, a fine pattern having a width of 5 nm to 70 nm, for example, a fine pattern having a width of 5 nm to 50 nm, for example, a fine pattern having a width of 5 nm to 40 nm, for example, a fine pattern having a width of 5 nm to 30 nm, or for example, a fine pattern having a width of 5 nm to 20 nm, the composition can be used in a photoresist process using light with a wavelength of 5 nm to 150 nm, for example, a photoresist process using light with a wavelength of 5 nm to 100 nm, for example, a photoresist process using light with a wavelength of 5 nm to 80 nm, for example, a photoresist process using light with a wavelength of 5 nm to 50 nm, for example, a photoresist process using light with a wavelength of 5 nm to 30 nm, or for example, a photoresist process using light with a wavelength of 5 nm to 20 nm. Therefore, by using the semiconductor photoresist composition according to an embodiment, extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5 nm can be realized.

[0066] According to another embodiment, there is provided a method for forming a pattern using the above-described semiconductor photoresist composition. For example, the formed pattern may be a photoresist pattern.

[0067] In one embodiment, another pattern forming method includes the steps of forming a layer to be etched on a substrate, applying the semiconductor photoresist composition described above on the layer to be etched to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and etching the layer to be etched using the photoresist pattern as an etching mask.

[0068] A method for forming a pattern using the above-described semiconductor photoresist composition will now be described with reference to Fig. 1. Fig. 1 is a cross-sectional view illustrating the method for forming a pattern using the semiconductor photoresist composition according to the present invention.

[0069] Referring to (a) of FIG. 1, a preferred etching target is provided. An example of the etching target may be a thin film 102 formed on a semiconductor substrate 100. The following description will be limited to the case where the etching target is the thin film 102. The surface of the thin film 102 is cleaned to remove contaminants remaining on the thin film 102. The thin film 102 may be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film.

[0070] Subsequently, a composition for forming a resist underlayer film to form a resist underlayer film 104 is coated by spin coating on the surface of the cleaned thin film 102. However, this is not intended to be limiting, 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.

[0071] The resist underlayer coating process can be omitted, and the case where the resist underlayer is coated will be described below.

[0072] Thereafter, a drying and baking process is carried out to form a resist underlayer film 104 on the thin film 102. The baking process can be carried out at about 100 to about 500°C, for example, about 100 to about 300°C.

[0073] The resist underlayer film 104 is formed between the substrate 100 and the photoresist film 106, and can prevent non-uniformity of the photoresist linewidth and interference with pattern formability when radiation reflected from the interface between the substrate 100 and the photoresist film 106 or from an interlayer hard mask is scattered into unintended photoresist regions.

[0074] 1(b), the above-described semiconductor photoresist composition is coated on the resist underlayer film 104 to form a photoresist film 106. The photoresist film 106 may be formed by coating the above-described semiconductor photoresist composition on a thin film 102 formed on a substrate 100 and then curing the composition through a heat treatment process.

[0075] More specifically, the step of forming a pattern using the semiconductor photoresist composition may include a process of applying the above-mentioned semiconductor photoresist composition onto the substrate 100 on which the thin film 102 has been formed by spin coating, slit coating, inkjet printing, or the like, and a process of drying the applied semiconductor photoresist composition to form a photoresist film 106.

[0076] The semiconductor photoresist composition has already been described in detail, so a duplicated description will be omitted.

[0077] Next, a first baking process is performed to heat the substrate 100 on which the photoresist film 106 is formed. The first baking process can be performed at a temperature of about 80°C to about 120°C.

[0078] Referring to FIG. 1(c), the photoresist film 106 is selectively exposed to light using a patterned mask 110.

[0079] As an example, examples of light that can be used in the exposure process include light with short wavelengths such as activation irradiation conductor i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), as well as light with high energy wavelengths such as EUV (Extreme ultraviolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0080] More specifically, according to an embodiment, the exposure light may be short wavelength light having a wavelength range of 5 nm to 150 nm, or may be light having a high energy wavelength such as EUV (Extreme ultraviolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0081] The exposed region 106b of the photoresist film 106 forms a polymer through a crosslinking reaction such as condensation between organometallic compounds, and thus has a different solubility from the unexposed region 106a of the photoresist film 106.

[0082] Next, a second baking process is performed on the substrate 100. The second baking process can be performed at a temperature of about 90° C. to about 200° C. By performing the second baking process, the exposed region 106b of the photoresist film 106 becomes difficult to dissolve in a developer.

[0083] 1(d) shows a photoresist pattern 108 formed by dissolving and removing the photoresist film 106a corresponding to the unexposed region using a developer. Specifically, the photoresist film 106a corresponding to the unexposed region is dissolved and removed using an organic solvent such as 2-heptanone, thereby completing the photoresist pattern 108 corresponding to the negative tone image.

[0084] As described above, the developer used in the pattern formation method according to an embodiment may be an organic solvent. Examples of the organic solvent used in the pattern formation method according to an 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, and combinations thereof.

[0085] However, the photoresist pattern according to an embodiment is not limited to being formed as a negative tone image, and may be formed as a positive tone image. In this case, examples of developers that can be used to form a positive tone image include quaternary ammonium hydroxide compositions such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof.

[0086] As described above, the photoresist pattern 108 formed by exposure to light having a wavelength such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), or ArF excimer laser (wavelength 193 nm), as well as high-energy light such as EUV (Extreme ultraviolet; wavelength 13.5 nm) or E-Beam (electron beam), may have a thickness of 5 nm to 100 nm. For example, the photoresist pattern 108 may have a thickness 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.

[0087] Meanwhile, the photoresist pattern 108 may have a half-pitch of about 50 nm or less, e.g., 40 nm or less, e.g., 30 nm or less, e.g., 20 nm or less, e.g., 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.

[0088] Then, the resist underlayer film 104 is etched using the photoresist pattern 108 as an etching mask, forming an organic layer pattern 112. The formed organic layer pattern 112 may also have a width corresponding to the photoresist pattern 108.

[0089] 1(e), the photoresist pattern 108 is used as an etching mask to etch the exposed thin film 102. As a result, the thin film is formed into a thin film pattern 114.

[0090] The thin film 102 can be etched by dry etching using an etching gas, such as CHF3, CF4, Cl2, BCl3, or a mixture thereof.

[0091] The thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process using an EUV light source in the previous exposure process may have a width corresponding to the photoresist pattern 108. For example, it may have a width of 5 nm to 100 nm, similar to the photoresist pattern 108. For example, the thin film pattern 114 formed by the exposure process using an EUV light source may have a width 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, may have a width of 20 nm or less. [Example]

[0092] The present invention will be described in more detail below through examples of the preparation of the above-mentioned semiconductor photoresist composition, but the technical features of the present invention are not limited to the following examples.

[0093] Synthesis of organometallic compounds Synthesis Example 1 340.7 g of t-butylSnPh and 300 g of propionic acid were placed in a 250 ml two-necked round-bottom flask and heated to reflux for 24 hours.

[0094] Unreacted propionic acid is removed under reduced pressure to obtain the compound represented by the following chemical formula 6. [ka]

[0095] Synthesis Example 2 Add 30 ml of anhydrous pentane to 10 g of t-AmylSnCl, maintain the temperature at 0°C, add 7.4 g of diethylamine and 6.1 g of ethanol, and stir at room temperature for 1 hour. After the reaction is complete, filter, concentrate, and vacuum dry to obtain the compound represented by the following formula 7. [ka]

[0096] Synthesis Example 3 10 g of dibutyltin dichloride was dissolved in 30 mL of ether, and then 70 mL of 1 M aqueous sodium hydroxide (NaOH) was added and stirred for 1 hour. After stirring, the resulting solid was filtered and washed three times with 25 mL of deionized water, and then dried under reduced pressure at 100°C to obtain an organometallic compound with a weight-average molecular weight of 1,500, represented by the following chemical formula 8. [ka]

[0097] (Production of semiconductor photoresist composition) Examples 1 to 11 and Comparative Examples 1 to 3 The Sn-containing organometallic compounds and carboxylic acid compounds represented by Chemical Formulae 6 to 8 obtained in Synthesis Examples 1 to 3 were dissolved in Propylene glycol methyl ether acetate (PGMEA) at a concentration of 3 wt % in the weight ratios shown in Table 1 below, and the solution was filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to produce semiconductor photoresist compositions according to Examples 1 to 11 and Comparative Examples 1 to 3.

[0098] [Table 1]

[0099] Evaluation 1: Sensitivity and Line Edge Roughness (LER) evaluation Each of the photoresist compositions according to the Examples and Comparative Examples was spin-coated at 1500 rpm for 30 seconds onto a 200 mm circular silicon wafer whose surface was coated with HMDS, baked at 110°C for 60 seconds (post-apply bake, PAB), and then left at room temperature (23±2°C) for 30 seconds.

[0100] Then, a linear array of 50 circular pads with a diameter of 500 μm was projected onto the wafer coated with the photoresist composition using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). The pad exposure time was adjusted so that an increased EUV dose was applied to each pad.

[0101] The resist was then post-exposure baked on a hotplate at 160 °C for 120 seconds. The baked film was developed in PGMEA solvent to form a negative tone image. A final hotplate bake at 150 °C for 2 minutes completed the process.

[0102] Using CD-SEM, the resist line width was measured in relation to changes in exposure dose (energy). The appropriate sensitivity for the exposure dose was confirmed from the resist line width values ​​formed differently at each exposure dose. The resolution was confirmed by measuring the resist line width formed by exposing a full wafer to the same dose at the confirmed appropriate sensitivity. In addition, line edge roughness (LER) was measured from the CD-SEM image, and the sensitivity and LER were evaluated according to the following criteria. The results are shown in Table 2.

[0103] [Sensitivity evaluation criteria] -A: 16 mJ / cm 2 less than -B: 16 mJ / cm 2 More than 18mJ / cm 2 less than -C: 18 mJ / cm 2 End

[0104] [LER evaluation criteria] -○: Less than 2 nm -△: 2nm or more and less than 5nm -X:5nm or more

[0105] Resolution Based -A: Less than 14.3 -B: 14.3 or more and less than 15.2 -C:15.2 or higher

[0106] [Table 2]

[0107] From the results in Table 2, it can be seen that the patterns formed using the semiconductor photoresist compositions according to Examples 1 to 11 exhibited superior sensitivity, LER and / or resolution compared to those of Comparative Examples 1 to 3.

[0108] Although specific embodiments of the present invention have been described and illustrated above, the present invention is not limited to the described embodiments, and it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modifications or variations should not be understood separately from the technical spirit or perspective of the present invention, and the modified embodiments should be considered to fall within the scope of the claims of the present invention. [Explanation of symbols]

[0109] 100...substrate, 102...thin film, 104...resist underlayer film, 106...photoresist film, 106a...unexposed region, 106b...exposed region, 108...photoresist pattern, 112...organic film pattern, 110...patterned mask, 114...thin film pattern.

Claims

1. Sn-containing organometallic compound; a carboxylic acid compound containing at least one aryl group and an unsaturated bond; and A composition for semiconductor photoresist, comprising a solvent.

2. 2. The composition for semiconductor photoresist of claim 1, wherein the carboxylic acid compound is represented by the following Chemical Formula 1 or Chemical Formula 2: 【Chemical 1】 In the above Chemical Formula 1, R １ ~R ３ are each independently hydrogen, halogen, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R １ ~R ３ at least one of is a substituted or unsubstituted C6 to C30 aryl group; L １ is a single bond or a substituted or unsubstituted C1-C10 alkylene group; 【Chemistry 2】 In the above Chemical Formula 2, R ４ is a substituted or unsubstituted C6-C30 aryl group, L ２ is a single bond or a substituted or unsubstituted C1-C10 alkylene group.

3. The R １ and R ２ At least one of the above or the R ３ and each independently represents a substituted or unsubstituted C6 to C30 aryl group.

4. The R １ and R ２ At least one of the above or the R ３ and the R ４ and each independently represent a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, or a substituted or unsubstituted triphenylene group.

5. 2. The semiconductor photoresist composition according to claim 1, wherein the carboxylic acid compound is one selected from the compounds listed in Group 1 below: 【Chemistry 3】

6. 2. The semiconductor photoresist composition according to claim 1, wherein the carboxylic acid compound is contained in an amount of 0.001 to 10% by weight based on 100% by weight of the semiconductor photoresist composition.

7. 2. The semiconductor photoresist composition according to claim 1, wherein the carboxylic acid compound is contained in an amount of 0.1 to 5% by weight based on 100% by weight of the semiconductor photoresist composition.

8. 2. The semiconductor photoresist composition according to claim 1, wherein the Sn-containing 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. 10. The semiconductor photoresist composition of claim 1, further comprising an additive selected from the group consisting of a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, and combinations thereof.

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

11. 2. The semiconductor photoresist composition according to claim 1, wherein the Sn-containing organometallic compound is represented by the following chemical formula 3: 【Chemistry 4】 In the above Chemical Formula 3, R ９ is selected from 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, and a substituted or unsubstituted C7 to C30 arylalkyl group; R １０ ~R １２ are each independently 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, a substituted or unsubstituted C7 to C30 arylalkyl group, alkoxy, and aryloxy (-OR ａ , where R ａ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), a carboxyl group (—O(C═O)R ｂ , R ｂ is 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), alkylamide or dialkylamide (—NR ｃ R ｄ , where R ｃ and R ｄ are each independently 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), amidato (—NR ｅ (C=OR ｆ ), where R ｅ and R ｆ are each independently 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), amidinato (—NR ｇ C (NR ｈ ) R ｉ , where R ｇ , R ｈ and R ｉ are each independently 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), alkylthio and arylthio (-SR ｊ , where R ｊ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof) or a thiocarboxyl group (—S(C═O)R ｋ , R ｋ is 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; R １０ ~R １２ At least one of the groups is alkoxy and aryloxy (—OR ａ , where R ａ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), a carboxyl group (—O(C═O)R ｂ , R ｂ is 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), alkylamide or dialkylamide (—NR ｃ R ｄ , where R ｃ and R ｄ are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, or an 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), amidato (—NR ｅ (C=OR ｆ ), where R ｅ and R ｆ are each independently 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), amidinato (—NR ｇ C (NR ｈ ) R ｉ , where R ｇ , R ｈ and R ｉ are each independently 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), alkylthio and arylthio (-SR ｊ , where R ｊ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), and a thiocarboxyl group (—S(C═O)R ｋ , R ｋ 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 R １０ ~R １２ At least one of the groups is alkoxy and aryloxy (—OR ａ , where R ａ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), and a carboxyl group (—O(C═O)R ｂ , R ｂ 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 R ９ is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group containing one or more double or triple bonds, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C4 to C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof; R ａ is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof; R ｂ 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. 2. The composition for semiconductor photoresist of claim 1, wherein the Sn-containing organometallic compound is represented by the following Chemical Formula 4 or Chemical Formula 5: 【Chemistry 5】 In the above Chemical Formula 4, R １３ is a C1 to C31 hydrocarbyl group, where 0<z≦2 and 0<(z+x)≦4; 【Chemistry 6】 In the above Chemical Formula 5, R １４ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 aliphatic unsaturated organic group containing one or more double or triple bonds, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof; X is sulfur (S), selenium (Se), or tellurium (Te); Y is -OR ｌ or -OC(=O)R ｍ and The R ｌ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R ｍ is 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; The a1, b1, c1 and d1 are each independently an integer of 1 to 20.

15. forming a film to be etched on a substrate; A step of applying the semiconductor photoresist composition according to any one of claims 1 to 14 onto the film to be etched to form a photoresist film; patterning the photoresist film to form a photoresist pattern; and A pattern forming method comprising: etching the target layer using the photoresist pattern as an etching mask.

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