Composition for semiconductor photoresist and pattern forming process using the same

Abstract

To provide a semiconductor photoresist composition and a pattern forming process using the composition, which can minimize occurrence of pattern defects and process delay effects, and to provide a photoresist film manufactured by the pattern forming process.SOLUTION: The invention relates to a composition for semiconductor photoresist containing an organometallic compound having a pentavalent metal with two radiation-sensitive functional groups and three hydrolyzable ligands, and a solvent, and to a pattern forming process using the same.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a semiconductor photoresist composition and a pattern forming 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 step in the semiconductor device manufacturing process.

[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, photospeed, 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 long-known fact in electron beam (e-beam) lithography. Chemically amplified (CA) photoresists, designed for high sensitivity, can experience additional difficulties 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 also experience roughness issues at small feature sizes, and experiments have shown 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, there is a demand in the semiconductor industry for 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 resistant to removal by developer compositions due to chemical modification through a non-chemically amplified mechanism. Inorganic compositions contain inorganic elements with higher EUV absorption than hydrocarbons, ensuring sensitivity even in non-chemically amplified mechanisms. They are also known to have reduced sensitivity 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 for 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 photospeeds 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, because they are complex mixtures, it is difficult to modify their structure to improve performance. Third, they must be developed using extremely high-concentration solutions, such as 25 wt% TMAH (tetramethylammonium hydroxide).

[0009] Recently, active research has been conducted on tin-containing molecules due to their excellent absorption of extreme ultraviolet light. 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 through 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, but further improvements in their patterning properties are required for commercialization. Summary of the Invention [Problem to be solved by the invention]

[0010] An embodiment of the present invention provides a composition for semiconductor photoresist that can minimize patterning defects and process delay effects.

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

[0012] Yet another embodiment of the present invention provides a photoresist film manufactured by the above patterning method. [Means for solving the problem]

[0013] A semiconductor photoresist composition according to one embodiment of the present invention comprises an organometallic compound containing a pentavalent metal having two radiation-sensitive functional groups and three hydrolyzable ligands, and a solvent.

[0014] A method for forming a pattern according to another embodiment of the present invention includes the steps of forming a layer to be etched on a substrate, applying the above-described semiconductor photoresist composition on the layer to be etched to form a photoresist layer, exposing and developing the photoresist layer to form a photoresist film having a photoresist pattern formed thereon, and etching the layer to be etched using the photoresist pattern as an etching mask.

[0015] A photoresist film according to yet another embodiment of the present invention can be manufactured by the above-described patterning method. [Effects of the Invention]

[0016] The semiconductor photoresist composition according to one embodiment of the present invention can significantly reduce reactivity with moisture after exposure, thereby mitigating deviations due to process delays. [Brief explanation of the drawings]

[0017] [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

[0018] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, in the description, descriptions of functions or configurations that are already known will be omitted in order to clarify the gist of the description.

[0019] In order to clarify the present description, parts unnecessary for the description have been omitted, and the same or similar components have been given 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 in the drawings.

[0020] In the drawings, the thickness of multiple layers and regions is exaggerated to clearly show them. For ease of explanation, the thickness of some layers and regions is exaggerated in the drawings. When a layer, film, region, plate, or other part is said to be "on" another part, this does not only mean that it is "directly on" that other part, but also includes the case where there is another part between them.

[0021] 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 saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted saturated or unsaturated alicyclic hydrocarbon group having 3 to 30 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms), -SiRR'R'' (wherein R, R', and R'' are each independently hydrogen, a substituted or unsubstituted "Unsubstituted" means that the hydrogen atoms are not substituted with other substituents and remain as hydrogen atoms.

[0022] 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 contain any double or triple bonds.

[0023] The alkyl group may be an alkyl group having 1 to 8 carbon atoms. For example, the alkyl group may be an alkyl group having 1 to 7 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. For example, the alkyl group having 1 to 5 carbon atoms 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.

[0024] In this description, unless otherwise defined, the term "cycloalkyl group" refers to a monovalent cyclic aliphatic saturated hydrocarbon group.

[0025] The cycloalkyl group may be a cycloalkyl group having 3 to 8 carbon atoms, for example, a cycloalkyl group having 3 to 7 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 3 to 5 carbon atoms, or a cycloalkyl group having 3 to 4 carbon atoms. 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.

[0026] As used herein, "aliphatically unsaturated organic group" refers to a hydrocarbon group containing bonds between carbon atoms in the molecule that are double bonds, triple bonds, or a combination thereof.

[0027] The aliphatic unsaturated organic group may be an aliphatic unsaturated organic group having 2 to 8 carbon atoms. For example, the aliphatic unsaturated organic group may be an aliphatic unsaturated organic group having 2 to 7 carbon atoms, an aliphatic unsaturated organic group having 2 to 6 carbon atoms, an aliphatic unsaturated organic group having 2 to 5 carbon atoms, or an aliphatic unsaturated organic group having 2 to 4 carbon atoms. For example, the aliphatic unsaturated organic group having 2 to 4 carbon atoms 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.

[0028] As used herein, "aryl group" refers to a cyclic substituent in which all elements have p-orbitals and these p-orbitals form conjugation, including monocyclic or fused-ring polycyclic (i.e., rings that share adjacent pairs of carbon atoms) functional groups.

[0029] 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, if the heteroaryl group contains two or more rings, the two or more rings may be fused to each other. If the heteroaryl group is a fused ring, each ring may contain 1 to 3 heteroatoms.

[0030] As used herein, unless otherwise defined, the term "alkenyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group and an aliphatic unsaturated alkenyl group containing one or more double bonds.

[0031] As used herein, unless otherwise defined, the term "alkynyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group and an aliphatic unsaturated alkynyl group containing one or more triple bonds.

[0032] Hereinafter, a semiconductor photoresist composition according to one embodiment will be described.

[0033] A semiconductor photoresist composition according to one embodiment of the present invention may include an organometallic compound containing a pentavalent metal having two radiation-sensitive functional groups and three hydrolyzable ligands, and a solvent.

[0034] The organometallic compound according to the present invention has two radiation-sensitive functional groups per metal atom, but also three hydrolyzable ligands, so that it can form a structurally stable spherical cluster. The blocking effect of the radiation-sensitive functional groups can significantly reduce reactivity with moisture after exposure, thereby mitigating deviations due to process delays.

[0035] The pentavalent metal can be selected from As, Sb and Bi.

[0036] In one embodiment, the pentavalent metal may be Sb.

[0037] The hydrolyzable ligands include alkoxy and aryloxy (—OR a , where R a is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), a carboxyl group (-O(CO)R b , R b is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylamide and dialkylamide (-NR c R d , where R c and R d are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), amidato (-NR e (CORf ), where R e and R f are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, 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 alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylthio and arylthio (-SR j , where R j is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), and a thiocarboxyl group (-S(CO)R k , R k can be selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof).

[0038] For example, the organometallic compound is represented by the following Chemical Formula 1: [ka]

[0039] In the above Chemical Formula 1, M 1 is selected from As, Sb and Bi; R 1 and R 2 are each independently selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms; X 1 ~X 3 are each independently selected from alkoxy and aryloxy (-OR a , where R a is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), a carboxyl group (-O(CO)R b , R b is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylamide and dialkylamide (-NR c R d , where R c and R dare each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), amidato (-NR e (COR f ), where R e and R f are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, 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 alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylthio and arylthio (-SR j , where R j is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), and a thiocarboxyl group (-S(CO)R k , R kis selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof).

[0040] As an example, the X 1 ~X 3 are each independently selected from alkoxy and aryloxy (-OR a , where R a is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof), a carboxyl group (-O(CO)R b , R b is hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof), alkylamide and dialkylamide (-NR c R d , where R c and R d are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), amidato (-NR e (COR f ), where R e and R fare each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, 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 alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof), alkylthio and arylthio (-SR j , where R j is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof), and a thiocarboxyl group (-S(CO)R k , R k can be selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof).

[0041] As a specific example, the X 1 ~X 3 are each independently selected from alkoxy and aryloxy (-OR a , where R ais a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof), a carboxyl group (-O(CO)R b , R b is hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof), and amidato (-NR e (COR f ), where R e and R f are each independently selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof.

[0042] For example, the R 1 and R 2 are each independently a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted tert-pentyl group, a substituted or unsubstituted ethenyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butenyl group, a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propynyl group, a substituted or unsubstituted butynyl group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted propoxy group, or a combination thereof; R a is a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted tert-pentyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted ethenyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butenyl group, a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propynyl group, a substituted or unsubstituted butynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted xylene group, a substituted or unsubstituted benzyl group, or a combination thereof; R b , R c , R d , R e , R f , R g , R h , R i , R j and R k are each independently a hydrogen atom, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted tert-pentyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted ethenyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butenyl group, a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propynyl group, a substituted or unsubstituted butynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted xylene group, a substituted or unsubstituted benzyl group, or a combination thereof.

[0043] In one embodiment, the semiconductor photoresist composition may further include at least one of an organometallic compound represented by the following Formula 2 and an organometallic compound represented by the following Formula 3:

[0044] [ka]

[0045] In the above Chemical Formula 2 and Chemical Formula 3, M 2 is selected from As, Sb and Bi; M 3 is selected from Sn, Pb and Ti; R 3 and R 4 are each independently selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms; X 4 ~X 10 are each independently selected from alkoxy and aryloxy (-OR a , where R a is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), a carboxyl group (-O(CO)R b , R bis hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylamide and dialkylamide (-NR c R d , where R c and R d are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), amidato (-NR e (COR f ), where R e and R f are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, 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 alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylthio and arylthio (-SR j , where R jis a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), and a thiocarboxyl group (-S(CO)R k , R k is selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof).

[0046] For example, the organometallic compound represented by Chemical Formula 1:at least one of the organometallic compound represented by Chemical Formula 2 and the organometallic compound represented by Chemical Formula 3 is contained in a weight ratio of 11:1 to 1:11.

[0047] Specifically, the organometallic compound represented by Chemical Formula 1:at least one of the organometallic compound represented by Chemical Formula 2 and the organometallic compound represented by Chemical Formula 3 is contained in a weight ratio of 5:1 to 1:5, or a weight ratio of 2:1 to 1:2.

[0048] For example, the above-mentioned M 2 can be Sb.

[0049] For example, the above-mentioned M 3 can be Sn.

[0050] The organometallic compound represented by Chemical Formula 1 has excellent sensitivity to high-energy light by strongly absorbing ultraviolet light at 13.5 nm.

[0051] In one embodiment, the semiconductor photoresist composition may contain the organometallic compound represented by Chemical Formula 1 in an amount of 0.5 wt % to 30 wt %, for example, 1 wt % to 30 wt %, 1 wt % to 25 wt %, for example, 1 wt % to 20 wt %, for example, 1 wt % to 15 wt %, for example, 1 wt % to 10 wt %, for example, 1 wt % to 5 wt %, based on 100 wt % of the semiconductor photoresist composition, but is not limited thereto. When the organometallic compound represented by Chemical Formula 1 is contained in an amount within the above range, the storage stability and etching resistance of the semiconductor photoresist composition are improved, and resolution characteristics are improved.

[0052] The semiconductor photoresist composition according to one embodiment of the present invention includes the organometallic compound described above, thereby providing a semiconductor photoresist composition having excellent sensitivity and pattern formability.

[0053] The solvent contained in the semiconductor photoresist composition according to one embodiment is 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.

[0054] In one embodiment, the semiconductor photoresist composition may further include a resin in addition to the organotin compound and solvent.

[0055] The resin may be a phenolic resin containing at least one aromatic moiety listed in Group 2 below. [ka]

[0056] The resin may have a weight average molecular weight of 500 to 20,000.

[0057] The resin may be contained in an amount of 0.1 wt % to 50 wt % based on the total content of the semiconductor photoresist composition.

[0058] When the resin is contained within the above content range, excellent etching resistance and heat resistance can be obtained.

[0059] Meanwhile, a semiconductor photoresist composition according to an embodiment preferably comprises the organometallic compound, solvent, and resin described above, although the semiconductor photoresist composition according to the above embodiment may further include an additive, if necessary.

[0060] For example, at least one additional additive selected from the group consisting of an alcohol-based compound, a thiol-based compound, a carboxylic acid compound, and a phosphoric acid compound may be further included.

[0061] More specific examples of the additional additive include, but are not limited to, ethanediol, succinic acid, and ethanephosphoric acid.

[0062] The additional additive may be included in an amount of 0.01 to 1 wt % based on the total content of the semiconductor photoresist composition.

[0063] For example, the additional additive may be included in an amount of 0.01 to 1 wt %, or 0.01 to 0.5 wt %, based on the total content of the semiconductor photoresist composition.

[0064] It may also contain other additives such as surfactants, crosslinkers, leveling agents, organic acids, quenchers, or combinations thereof.

[0065] The surfactant may be, for example, but not limited to, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, or a combination thereof.

[0066] 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, and polymer-based crosslinking agents. Examples of crosslinking agents having at least two crosslink-forming substituents that can be used include methoxymethylated glycoluril, butoxymethylated glycoluril, 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.

[0067] The leveling agent is used to improve coating flatness during printing, and any known leveling agent that is commercially available can be used.

[0068] The organic acid can be, but is not limited to, p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, sulfonium fluoride salts, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or combinations thereof.

[0069] The quencher can be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0070] The amounts of these other additives used can be easily adjusted depending on the desired physical properties, and they can also be omitted.

[0071] 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; 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; and silane compounds containing a carbon-carbon unsaturated bond, such as trimethoxy[3-(phenylamino)propyl]silane.

[0072] The semiconductor photoresist composition may not cause pattern collapse even when forming a pattern having a high aspect ratio. Therefore, 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 70 nm, for example, a photoresist process using light with a width of 5 nm to 50 nm, for example, a photoresist process using light with a wavelength of 5 nm to 40 nm, for example, a photoresist process using light with a wavelength of 5 nm to 30 nm, for example, a photoresist process using light with a wavelength of 5 nm to 20 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 one embodiment, extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5 nm can be realized.

[0073] According to another embodiment, there is provided a method for forming a pattern using the semiconductor photoresist composition. For example, the formed pattern may be a photoresist pattern.

[0074] According to one embodiment, a method for forming a pattern includes forming a layer to be etched on a substrate; applying the semiconductor photoresist composition on the layer to be etched to form a photoresist layer; exposing and developing the photoresist layer to form a photoresist film having a photoresist pattern formed thereon; and etching the layer to be etched using the photoresist pattern as an etching mask.

[0075] Hereinafter, a method for forming a pattern using the semiconductor photoresist composition will be described with reference to Fig. 1. Fig. 1 is a cross-sectional view illustrating a method for forming a pattern using the semiconductor photoresist composition according to the present invention.

[0076] Referring to FIG. 1(a), first, an etching target is prepared. 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.

[0077] Next, a composition for forming a resist underlayer film is coated by spin coating on the surface of the cleaned thin film 102 to provide a resist underlayer film 104. However, this embodiment is not limited thereto, and various known coating methods, such as spray coating, dip coating, knife edge coating, and printing methods, such as inkjet printing and screen printing, may also be used.

[0078] The resist underlayer film coating step can be omitted, and the following description will be made of the case where the resist underlayer film is coated.

[0079] Thereafter, drying and baking steps are performed to form a resist underlayer film 104 on the thin film 102. The baking treatment can be performed at about 100 to about 500°C, for example, about 100 to about 300°C.

[0080] 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 disruption of 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.

[0081] 1(b), the 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 semiconductor photoresist composition on a thin film 102 formed on a substrate 100 and then curing the composition through a heat treatment process.

[0082] More specifically, the step of forming a pattern using the semiconductor photoresist composition may include a step of applying the semiconductor photoresist composition onto the substrate 100 on which the thin film 102 has been formed by spin coating, slit coating, inkjet printing, etc., and a step of drying the applied semiconductor photoresist composition to form a photoresist film 106.

[0083] The photoresist film may at least partially contain moieties represented by the following Chemical Formulas 4-1 to 4-5. [ka]

[0084] In the above Chemical Formula 4-1 to Chemical Formula 4-5, M 1 and M 2 are each independently selected from As, Sb, and Bi; M 3 is selected from Sn, Pb and Ti; R 1 ~R 4are each independently selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms.

[0085] The semiconductor photoresist composition has already been explained in detail, so a duplicate explanation will be omitted.

[0086] 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.

[0087] Referring to FIG. 1(c), the photoresist film 106 is selectively exposed to light using a patterned mask 110.

[0088] For example, examples of light that can be used in the exposure process include light with short wavelengths such as activation irradiation 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).

[0089] More specifically, the exposure light according to one embodiment 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).

[0090] The exposed region 106b of the photoresist film 106 has a different solubility from the unexposed region 106a of the photoresist film 106 by forming a polymer through a crosslinking reaction such as condensation between organometallic compounds.

[0091] 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 less soluble in a developer.

[0092] 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.

[0093] 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.

[0094] However, the photoresist pattern according to an embodiment is not necessarily limited to being formed as a negative tone image, and may also be formed as a positive tone image. In this case, 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.

[0095] 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 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, 5 nm to 20 nm, or 5 nm to 10 nm.

[0096] 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., 10 nm or less, and a pitch with a line width roughness of about 5 nm or less, about 3 nm or less, about 2 nm or less, or about 1 nm or less.

[0097] According to another embodiment, a photoresist film manufactured by the above-described pattern forming method can be provided.

[0098] Next, the resist underlayer 104 is etched using the photoresist pattern 108 formed on the photoresist film as an etching mask. This etching process forms an organic layer pattern 112. The formed organic layer pattern 112 may also have a width corresponding to the photoresist pattern 108.

[0099] 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.

[0100] The thin film 102 can be etched by dry etching using an etching gas, such as CHF3, CF4, Cl2, BCl3, or a mixture thereof.

[0101] The thin film pattern 114 formed using the photoresist pattern 108 formed by the previous exposure process using an EUV light source 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]

[0102] The present invention will be described in more detail below with reference to examples of preparing the above-mentioned semiconductor photoresist composition, but the technical features of the present invention are not limited to these examples.

[0103] (synthesis of organometallic compounds) Synthesis Example 1: Synthesis of Compound P-1 (Diphenylantimony trichloride) A 250 mL single-neck round-bottom flask was charged with 10.0 g (28.3 mmol) of triphenylantimony and 3.23 g (14.2 mmol) of antimony trichloride, stirred in a 70°C oil bath, and then reacted at room temperature (25 ± 3°C) for 2 days. After adding 100 mL of dichloromethane (DCM) and completely dissolving, 42.5 mL (42.5 mmol) of a 1 M DCM solution of surfuryl chloride was slowly added dropwise. After stirring for 24 hours, 80 mL of DCM was added and the mixture was placed in a -20°C freezer for one day to yield 8.3 g of crystals.

[0104] Synthesis Example 2: Synthesis of Compound P-2 (Diphenylantimony tripropionate) 2.09 g (5.47 mmol) of diphenylantimony trichloride, the compound of Synthesis Example 1, was dissolved in 100 ml of toluene, and then excess propionic acid and 2.02 g (18.0 mmol) of potassium propionate were added sequentially. After nitrogen purging, the mixture was stirred in a reflux state in a 110°C oil bath for one day.

[0105] The solvent and propionic acid were then removed at low pressure at 80°C, and the residue was dissolved in 50 ml of DCM and filtered. The filtered solution was stripped of DCM under nitrogen to give 2.7 g of a pale yellow solid.

[0106] Synthesis Example 3: Synthesis of Compound P-3 (monophenylantimony tetrachloride) A 250 mL single-neck round-bottom flask was charged with 5.0 g (14.2 mmol) of triphenylantimony and 6.4 g (28.4 mmol) of antimony trichloride. The mixture was stirred in a 70°C oil bath and then reacted at room temperature for 2 days. After adding 120 mL of dichloromethane (DCM) and completely dissolving the mixture, 42.5 mL (42.5 mmol) of a 1 M DCM solution of surfuryl chloride was slowly added dropwise. After stirring for 24 hours, 100 mL of DCM was added and the mixture was placed in a -20°C freezer for one day to yield 6.2 g of crystals.

[0107] Synthesis Example 4: Synthesis of Compound P-4 (monophenylantimony tetrapropionate) 2.00 g (5.87 mmol) of monophenylantimony tetrachloride, the compound from Synthesis Example 3, was dissolved in 100 ml of toluene, followed by the addition of excess propionic acid and 2.11 g (18.8 mmol) of potassium propionate. After purging with nitrogen, the mixture was stirred in a reflux state in an oil bath at 110°C for one day. The solvent and propionic acid were then removed at low pressure at 80°C, and the residue was dissolved in 50 ml of DCM and filtered. The DCM was removed from the filtered solution under nitrogen, yielding 2.1 g of a pale yellow solid.

[0108] Synthesis Example 5: Synthesis of Compound P-5 (monophenyltin tripropionate) Tetraphenyltin (3.0 g, 7.02 mmol) and tin tetrachloride (5.4 g, 21.1 mmol) were placed in a 250 mL single-neck round-bottom flask and stirred in an 80°C oil bath, then reacted at room temperature for two days. Then, 20.8 g (281 mmol) of propionic acid was added and stirred at 130°C under reflux for one day. The solvent and propionic acid were then removed at low pressure and 100°C, yielding 11.3 g of a pale yellow viscous liquid.

[0109] Synthesis Example 6: Synthesis of Compound P-6 (dibenzyl phenyl antimony) 5.0 g (14.2 mmol) of triphenylantimony and 6.4 g (28.4 mmol) of antimony trichloride were placed in a 250 mL single-neck round-bottom flask and stirred in a 70 °C oil bath, then reacted at room temperature for 2 days. After dissolving the mixture in 40 mL of anhydrous tetrahydrofuran (THF), 85.2 mL (85.2 mmol) of a 1 M benzyl magnesium chloride THF solution was slowly added dropwise at 0 °C. The mixture was then stirred at room temperature for 1 day, and the THF was removed under low pressure to yield 15.1 g of a solid.

[0110] Synthesis Example 7: Synthesis of Compound P-7 (dibenzyl antimony trichloride) In a 100 mL single-neck round-bottom flask, 5.0 g (12.2 mmol) of dibenzyl phenyl antimony (Synthesis Example 6) was dissolved in 30 mL of DCM, and then 6.1 mL (12.2 mmol) of a 2 M HCl diethyl ether solution was slowly added dropwise at -78°C. After stirring at room temperature for one day, 12.2 mL (12.2 mmol) of a 1 M surfuryl chloride DCM solution was slowly added dropwise. After stirring for 24 hours, 80 mL of DCM was added, and the mixture was then placed in a freezer at -20°C for one day to yield 4.3 g of crystals.

[0111] Synthesis Example 8: Synthesis of Compound P-8 (dibenzyl antimony tripropionate) In Synthesis Example 2, dibenzyl antimony trichloride of Synthesis Example 7 was used in place of diphenylantimony trichloride of Synthesis Example 1, to obtain dibenzyl antimony tripropionate, a pale yellow solid.

[0112] Synthesis Example 9: Synthesis of Compound P-9 (benzyl diphenyl antimony) 10.0 g (28.4 mmol) of triphenylantimony and 3.23 g (14.2 mmol) of antimony trichloride were placed in a 250 mL single-neck round-bottom flask and stirred in a 70 °C oil bath, then reacted at room temperature for 2 days. The mixture was then dissolved in 40 mL of anhydrous tetrahydrofuran (THF), and 42.6 mL (42.6 mmol) of a 1 M benzyl magnesium chloride THF solution was slowly added dropwise at 0 °C. The mixture was then stirred at room temperature for 1 day, and the THF was removed under low pressure to yield 12.7 g of a solid.

[0113] Synthesis Example 10: Synthesis of Compound P-10 (monobenzyl antimony tetrachloride) In a 100 mL single-neck round-bottom flask, 4.65 g (12.2 mmol) of benzyl diphenyl antimony (Synthesis Example 9) was dissolved in 30 mL of DCM, and then 6.1 mL (12.2 mmol) of a 2 M HCl diethyl ether solution was slowly added dropwise at -78°C. After stirring at room temperature for one day, 12.2 mL (12.2 mmol) of a 1 M surfuryl chloride DCM solution was slowly added dropwise. After stirring for 24 hours, 80 mL of DCM was added, and the mixture was then placed in a freezer at -20°C for one day to yield 3.1 g of crystals.

[0114] Synthesis Example 11: Synthesis of Compound P-11 (monobenzylantimony tetrapropionate) In Synthesis Example 4, monobenzyl antimony tetrachloride of Synthesis Example 10 was used in place of monophenylantimony tetrachloride of Synthesis Example 3, and monobenzyl antimony tetrapropionate, a pale yellow solid, was obtained in 65% yield.

[0115] Synthesis Example 12: Synthesis of Compound P-12 (Diphenylantimony tripropoxide) 2.09 g (5.47 mmol) of diphenylantimony trichloride, the compound of Synthesis Example 1, was dissolved in 100 ml of anhydrous ether, and 1.35 g (16.4 mmol) of sodium propoxide was slowly added dropwise at 0° C. The mixture was then stirred at room temperature for one day.

[0116] The solvent was then removed at low pressure at 50°C, and the residue was dissolved in 50 ml of DCM and filtered. The filtered solution was stripped of DCM under nitrogen to give 2.3 g of a pale yellow solid.

[0117] (Production of semiconductor photoresist composition) Examples 1 to 17 and Comparative Examples 1 to 5 The organometallic compounds obtained in Synthesis Examples 1 to 12 were dissolved in xylene at a concentration of 3 wt % according to the compositions shown in Table 1, and the solution was filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to prepare semiconductor photoresist compositions.

[0118] [Table 1]

[0119] 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 had been deposited 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.

[0120] Then, a linear array of 50 circular pads, each 500 μm in diameter, was projected onto the wafer coated with the photoresist composition using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). Pad exposure time was adjusted so that an increased EUV dose was applied to each pad.

[0121] The resist and substrate were then exposed and baked on a hot plate at 160°C for 120 seconds. The baked film was developed with PGMEA solvent to form a negative tone image. The process was terminated by a final hot plate bake at 150°C for 2 minutes.

[0122] The remaining resist thickness of the exposed pad was measured using an ellipsometer. The remaining thickness was measured for each exposure dose, and graphed as a function of exposure dose to measure Eop (energy of optimum). The sensitivity was evaluated according to the following criteria, and the results are shown in Table 2.

[0123] The line edge roughness (LER) of the line and space pattern was measured using an electron microscope, and the results were evaluated according to the following criteria and are shown in Table 2.

[0124] [Sensitivity evaluation criteria] -A: Relative value to Eop of Comparative Example 1 is less than 50% -B: The relative value to Eop of Comparative Example 1 is 50% or more and less than 100% -C: Relative value to Eop of Comparative Example 1 is 100% or more [Line Edge Roughness (LER) Evaluation Criteria] -A: 4nm or less -B: More than 4nm and less than 7nm -C: More than 7nm

[0125] Evaluation 2: Process delay stability evaluation After the process was completed, the pattern wafer was formed with a line / space CD pattern, and then transferred to a CD-SEM measuring device (GC-9380, manufactured by Hitachi) to measure the critical dimension (CD) size of the mask pattern where the half-pitch was 14 nm. The minimum value of the space CD, which is the distance between lines, was measured, and the CD size change rate calculated using Equation 1 below was measured according to the following criteria, and the results are shown in Table 2. The measurement error was ±1.0 nm.

[0126] <Expression 1> ΔCD: CD without post-exposure delay - CD with 30-minute post-exposure delay [Evaluation criteria] -AA: ΔCD less than 3% -A: ΔCD 3% or more and less than 5% -B: ΔCD 5% or more and less than 10% -C:ΔCD10% or more

[0127] [Table 2]

[0128] From the results in Table 2, it can be seen that the patterns formed using the semiconductor photoresist compositions of Examples 1 to 17 exhibit superior sensitivity and / or LER, and stability against process delay, compared to Comparative Examples 1 to 5.

[0129] Although specific embodiments of the present invention have been described and illustrated above, it will be apparent to those skilled in the art that the present invention is not limited to the described embodiments and that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modifications and variations should not be understood individually from the technical spirit and 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]

[0130] 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. an organometallic compound containing a pentavalent metal having two radiation-sensitive functional groups and three hydrolyzable ligands; and A composition for semiconductor photoresist, comprising a solvent.

2. 2. The semiconductor photoresist composition according to claim 1, wherein the pentavalent metal is one selected from the group consisting of As, Sb, and Bi.

3. The hydrolyzable ligands are alkoxy and aryloxy (—OR ａ , where R ａ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), a carboxyl group (—O(CO)R ｂ , R ｂ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylamides and dialkylamides (—NR ｃ R ｄ , where R ｃ and R ｄ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), amidato (—NR ｅ (COR ｆ ), where R ｅ and R ｆ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, 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 alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylthio and arylthio (-SR ｊ , where R ｊ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), and a thiocarboxyl group (—S(CO)R ｋ , R ｋ is one selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof.

4. 2. The composition for semiconductor photoresist of claim 1, wherein the organometallic compound is represented by the following chemical formula 1: 【Chemical 1】 In the above Chemical Formula 1, M １ is selected from As, Sb and Bi; R １ and R ２ are each independently selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms; X １ ~X ３ are each independently selected from alkoxy and aryloxy (—OR ａ , where R ａ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), a carboxyl group (—O(CO)R ｂ , R ｂ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylamides and dialkylamides (—NR ｃ R ｄ , where R ｃ and R ｄ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), amidato (—NR ｅ (COR ｆ ), where R ｅ and R ｆ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, 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 alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylthio and arylthio (-SR ｊ , where R ｊ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), and a thiocarboxyl group (—S(CO)R ｋ , R ｋ is selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof.

5. The X １ ~X ３ are each independently selected from alkoxy and aryloxy (—OR ａ , where R ａ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof), a carboxyl group (—O(CO)R ｂ , R ｂ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof), alkylamides and dialkylamides (-NR ｃ R ｄ , where R ｃ and R ｄ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), amidato (—NR ｅ (COR ｆ ), where R ｅ and R ｆ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, 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 alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof), alkylthio and arylthio (-SR ｊ , where R ｊ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof), and a thiocarboxyl group (—S(CO)R ｋ , R ｋ is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof.

6. The X １ ~X ３ are each independently selected from alkoxy and aryloxy (—OR ａ , where R ａ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof), a carboxyl group (—O(CO)R ｂ , R ｂ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof), and amidato (—NR ｅ (COR ｆ ), where R ｅ and R ｆ are each independently selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof.

7. The R １ and R ２ are each independently a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted tert-pentyl group, a substituted or unsubstituted ethenyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butenyl group, a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propynyl group, a substituted or unsubstituted butynyl group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted propoxy group, or a combination thereof; The R ａ is a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted tert-pentyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted ethenyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butenyl group, a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propynyl group, a substituted or unsubstituted butynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted xylene group, a substituted or unsubstituted benzyl group, or a combination thereof; R ｂ , R ｃ , R ｄ , R ｅ , R ｆ , R ｇ , R ｈ , R ｉ , R ｊ and R ｋ are each independently a hydrogen atom, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted tert-pentyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted ethenyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butenyl group, a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propynyl group, a substituted or unsubstituted butynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted xylene group, a substituted or unsubstituted benzyl group, or a combination thereof.

8. 2. The semiconductor photoresist composition according to claim 1, further comprising at least one of an organometallic compound represented by the following Chemical Formula 2 and an organometallic compound represented by the following Chemical Formula 3: 【Chemistry 2】 In Chemical Formula 2 and Chemical Formula 3, M ２ is selected from As, Sb and Bi; M ３ is selected from Sn, Pb and Ti; R ３ and R ４ are each independently selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms; X ４ ~X １０ are each independently selected from alkoxy and aryloxy (—OR ａ , where R ａ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), a carboxyl group (—O(CO)R ｂ , R ｂ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylamides and dialkylamides (—NR ｃ R ｄ , where R ｃ and R ｄ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), amidato (—NR ｅ (COR ｆ ), where R ｅ and R ｆ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, 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 alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylthio and arylthio (-SR ｊ , where R ｊ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), and a thiocarboxyl group (—S(CO)R ｋ , R ｋ is selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof.

9. 9. The composition for semiconductor photoresist according to claim 8, wherein the organometallic compound represented by Chemical Formula 1:at least one of the organometallic compound represented by Chemical Formula 2 and the organometallic compound represented by Chemical Formula 3 is contained in a weight ratio of 11:1 to 1:

11.

10. 5. The composition for semiconductor photoresist of claim 4, wherein the organometallic compound represented by Chemical Formula 1 is contained in an amount of 0.5 to 30 wt % based on 100 wt % of the composition for semiconductor photoresist.

11. 2. The semiconductor photoresist composition according to claim 1, further comprising at least one additional additive selected from the group consisting of an alcohol-based compound, a thiol-based compound, a carboxylic acid compound, and a phosphoric acid compound.

12. 10. The semiconductor photoresist composition of claim 1, further comprising other additives such as a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, or a combination thereof.

13. forming a film to be etched on a substrate; applying the semiconductor photoresist composition according to any one of claims 1 to 12 onto the film to be etched to form a photoresist film; exposing and developing the photoresist film to form a photoresist film having a photoresist pattern formed thereon; and etching the target layer using the photoresist pattern as an etching mask.

14. The pattern formation method according to claim 13, wherein the photoresist film partially contains at least one of moieties represented by the following Chemical Formulas 4-1 to 4-5: 【Chemistry 3】 In Chemical Formula 4-1 to Chemical Formula 4-5, M １ and M ２ are each independently selected from As, Sb, and Bi; M ３ is selected from Sn, Pb and Ti; R １ ~R ４ are each independently selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms.

15. A photoresist film produced by the pattern formation method according to claim 13.

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