Semiconductor photoresist composition and pattern forming method using the same

Abstract

To provide a semiconductor photoresist composition excellent in coating properties and LER, and a pattern forming method using the same.SOLUTION: The present invention relates to: a semiconductor photoresist composition which contains a first organometallic compound represented by chemical formula 1, a second organometallic compound represented by chemical formula 2, 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 that has excellent coating properties and LER.

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

[0012] A composition for semiconductor photoresist according to an embodiment of the present invention includes a first organometallic compound represented by the following Chemical Formula 1, a second organometallic compound represented by the following Chemical Formula 2, and a solvent. [ka] [ka] In the above Chemical Formula 1 and Chemical Formula 2, M 1 and M 2 are each independently Sn or Te, R 1 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, or -L a -OR a (where L a is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and R ais a substituted or unsubstituted C1-C20 alkyl group, R 2 is a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group, X 1 and X 2 are each independently alkoxy and aryloxy (-OR b , where R b 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, a substituted or unsubstituted C7 to C30 arylalkyl group, or a combination thereof), a carboxyl group (-O(CO)R c , R c 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, a substituted or unsubstituted C7 to C30 arylalkyl group, or a combination thereof), alkylamide or dialkylamide (-NR d R e , where R d and R e 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, a substituted or unsubstituted C7 to C30 arylalkyl group, or a combination thereof), amidato (-NR f (COR g ), where R f and R gare 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, a substituted or unsubstituted C7 to C30 arylalkyl group, or a combination thereof), amidinato (-NR h C(NR i )R j , where R h , R i and R j 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, a substituted or unsubstituted C7 to C30 arylalkyl group, or a combination thereof), alkylthio and arylthio (-SR k , where R k 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, a substituted or unsubstituted C7 to C30 arylalkyl group, or a combination thereof) and a thiocarboxyl group (-S(CO)R l , R l is selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, or a combination thereof; a, b, c, and d are each independently an integer of 1 to 5; a+b is an integer between 4 and 6, c+d is an integer between 4 and 6.

[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 may provide a photoresist pattern with excellent coating properties and LER. [Brief explanation of the drawings]

[0015] [Figure 1] 1 is a cross-sectional view 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. However, in the 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 replaced with another substituent and remains a hydrogen atom.

[0020] As used herein, unless otherwise defined, an "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 C10 alkyl group. For example, the alkyl group may be a C1 to C8 alkyl group, 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 C10 cycloalkyl group, such as a C3 to C8 cycloalkyl group, a C3 to C7 cycloalkyl group, or a C3 to C6 cycloalkyl group. For example, the cycloalkyl group may be, but is not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] In the chemical formulae described herein, t-Bu refers to a tert-butyl group.

[0028] Hereinafter, a semiconductor photoresist composition according to an embodiment will be described.

[0029] A composition for semiconductor photoresist according to an embodiment of the present invention includes a first organometallic compound represented by the following Chemical Formula 1, a second organometallic compound represented by the following Chemical Formula 2, and a solvent. [ka] [ka] In the above Chemical Formula 1 and Chemical Formula 2, M 1 and M 2 are each independently Sn or Te, R 1 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, or -L a -OR a (where L a is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and R a is a substituted or unsubstituted C1-C20 alkyl group, R 2 is a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group, X 1 and X 2 are each independently alkoxy and aryloxy (-OR b , where R bis 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, or a combination thereof), a carboxyl group (-O(CO)R c , R c 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, a substituted or unsubstituted C7 to C30 arylalkyl group, or a combination thereof), alkylamide or dialkylamide (-NR d R e , where R d and R e 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, a substituted or unsubstituted C7 to C30 arylalkyl group, or a combination thereof), amidato (-NR f (COR g ), where R f and R g 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, a substituted or unsubstituted C7 to C30 arylalkyl group, or a combination thereof), amidinato (-NR h C(NR i )R j , where R h , R i and R jare 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, a substituted or unsubstituted C7 to C30 arylalkyl group, or a combination thereof), alkylthio and arylthio (-SR k , where R k 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, a substituted or unsubstituted C7 to C30 arylalkyl group, or a combination thereof) and a thiocarboxyl group (-S(CO)R l , R l is selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, or a combination thereof; a, b, c, and d are each independently an integer of 1 to 5; a+b is an integer between 4 and 6, c+d is an integer between 4 and 6.

[0030] The present invention blends two organometallic compounds, a first organometallic compound and a second organometallic compound, which have high EUV absorbance, to ensure stability against moisture and heat without the need for additional organic additives. Furthermore, by reducing crystallinity through the introduction of various ligands, it is possible to achieve excellent coatability and LER.

[0031] In particular, in the case of a chain organometallic compound having a uniform structure, the compound may be highly crystalline during coating and may not be coated uniformly. However, when a cyclic organometallic compound is used in combination as in the present invention, crystal formation during coating is difficult, resulting in improved coatability.

[0032] For example, the first organometallic compound and the second organometallic compound may be contained in a weight ratio of 90:10 to 40:60.

[0033] More specifically, the first organometallic compound and the second organometallic compound may be contained in a weight ratio of 80:20 to 40:60, for example, 70:30 to 40:60.

[0034] As an example, the above-mentioned R 1 is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, or -L a -OR a (where L a is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and R a is a substituted or unsubstituted C1-C20 alkyl group, R 2 is a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, X 1 and X 2 are each independently alkoxy and aryloxy (-OR b , where R b is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 arylalkyl group, or a combination thereof), a carboxyl group (-O(CO)Rc , R c is hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C7-C20 arylalkyl group, or a combination thereof), alkylamide or dialkylamide (-NR d R e , where R d and R e are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 arylalkyl group, or a combination thereof), amidato (-NR f (COR g ), where R f and R g are each independently hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C7-C20 arylalkyl group, or a combination thereof), or amidinato (-NR h C(NR i )R j , where R h , R i and R j are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 arylalkyl group, or a combination thereof), alkylthio and arylthio (-SR k, where R k is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 arylalkyl group, or a combination thereof) and a thiocarboxyl group (-S(CO)R l , R l is selected from hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C7-C20 arylalkyl group, or a combination thereof.

[0035] As a specific example, the R 1 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 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 2is 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 phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted xylene group, a substituted or unsubstituted pyridine group, a substituted or unsubstituted pyrrolidine group, a substituted or unsubstituted piperidine group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted tetrahydrofuranyl group, a substituted or unsubstituted pyranyl group, a substituted or unsubstituted tetrahydropyranyl group, a substituted or unsubstituted dioxane, a substituted or unsubstituted morpholine group, or a combination thereof; R b 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 c , R d , R e , R f , R g , R h , R i , R j , R k , and R lare 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 substituted benzyl group, or a combination thereof.

[0036] The second organometallic compound can be selected from the compounds listed in Group 2 below. [ka] [ka]

[0037] The first organometallic compound can be selected from the compounds listed in Group 1 below. [ka] The organometallic compound has strong absorption of extreme ultraviolet light at 13.5 nm and has excellent sensitivity to light having high energy.

[0038] In a semiconductor photoresist composition according to an embodiment, the first organometallic compound and the second organometallic compound may be contained in an amount of 1 wt % to 30 wt %, for example, 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. When the organometallic compounds are contained in an amount within this range, the storage stability and etching resistance of the semiconductor photoresist composition are improved, and resolution characteristics are improved.

[0039] A semiconductor photoresist composition according to an embodiment of the present invention may provide a semiconductor photoresist composition having excellent sensitivity and pattern formability by including the first organometallic compound and the second organometallic compound described above.

[0040] 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.

[0041] In an embodiment, the semiconductor photoresist composition may further include a resin in addition to the first organometallic compound, the second organometallic compound, and the solvent.

[0042] The resin may be a phenolic resin containing at least one aromatic moiety listed in Group 3 below. [ka] The resin may have a weight average molecular weight of 500 to 20,000.

[0043] 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.

[0044] When the resin is contained in the above content range, excellent etching resistance and heat resistance can be obtained.

[0045] Meanwhile, a semiconductor photoresist composition according to an embodiment preferably comprises the first organometallic compound, the second organometallic compound, a solvent, and a resin. However, the semiconductor photoresist composition according to the embodiment may further include an additive, if desired. Examples of the additive include a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, or a combination thereof.

[0046] The surfactant may be, for example, but not limited to, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, or a combination thereof.

[0047] 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 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)tetramethyldisiloxate, methoxymethylated urea, butoxymethylated urea, and methoxymethylated thiourea.

[0048] The leveling agent is used to improve the flatness of the coating during printing, and any known leveling agent that is commercially available can be used.

[0049] 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.

[0050] The quencher may be diphenyl(p-toluyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0051] The amount of these additives used can be easily adjusted depending on the desired physical properties, and they can also be omitted.

[0052] The semiconductor photoresist composition may 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.

[0053] The semiconductor photoresist composition may form a pattern having a high aspect ratio without causing pattern collapse. 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 width of 5 nm to 40 nm, for example, a photoresist process using light with a width of 5 nm to 30 nm, for example, a photoresist process using light with a wavelength of 5 nm to 20 nm, or 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.

[0054] 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.

[0055] In one embodiment, another pattern formation 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.

[0056] 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.

[0057] Referring to FIG. 1(a), a preferred etching target is provided. An example of the etching target may be a thin film 102 formed on a semiconductor substrate 100. Hereinafter, only the case where the etching target is the thin film 102 will be described. 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.

[0058] Subsequently, 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 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.

[0059] The resist underlayer coating process can be omitted, and the case where the resist underlayer is coated will be described below.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] The semiconductor photoresist composition has already been described in detail, so a duplicated description will be omitted.

[0065] 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.

[0066] Referring to FIG. 1(c), the photoresist film 106 is selectively exposed to light using a patterned mask 110.

[0067] For 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).

[0068] More specifically, the exposure light according to an 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).

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] However, the photoresist pattern according to an embodiment is not limited to being formed as a negative tone image, and may also 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.

[0074] 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.

[0075] 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 having 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.

[0076] 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.

[0077] 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.

[0078] The thin film 102 can be etched by dry etching using an etching gas, such as CHF3, CF4, Cl2, BCl3, or a mixture thereof.

[0079] 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]

[0080] The present invention will be described in more detail below through examples of preparing the above-mentioned semiconductor photoresist composition, but the technical features of the present invention are not limited to these examples.

[0081] (Synthesis of the first organometallic compound) Synthesis Example 1 Dissolve Ph3SnCl (20 g, 51.9 mmol) in 100 mL of anhydrous tetrahydrofuran (THF) in a 250 mL two-neck round-bottom flask and cool to 0°C using an ice bath. Then, slowly add 1 M tert-butylmagnesium bromide (62.3 mmol) in THF. After the addition is complete, stir at 25°C for 12 hours. After vacuum distillation, slowly add 50 mL of isobutyric acid at 25°C and heat to reflux for 12 hours. After cooling to 25°C, vacuum distill the isobutyric acid to obtain the compound represented by the following formula 1a. [ka]

[0082] Synthesis Example 2 Dissolve Ph3SnCl (20 g, 51.9 mmol) in 100 mL of anhydrous tetrahydrofuran (THF) in a 250 mL two-neck round-bottom flask and cool to 0°C using an ice bath. Then, slowly add isopropylmagnesium bromide 1 M THF solution (62.3 mmol). After the addition is complete, stir at 25°C for 12 hours. After vacuum distillation, dissolve in 50 mL of CHCl2 and add 3 equivalents (155.7 mmol) of 2 M HCl diethyl ether solution slowly at -78°C for 30 minutes. After stirring at 25°C for 12 hours, concentrate the solvent, vacuum distill, and then dissolve again in 50 mL of CHCl2. Add 3 equivalents (51.9 mmol) of silver tert-butoxide dropwise at 0°C. Filter and remove the resulting solid, and distill the filtrate to obtain the compound represented by formula 2a. [ka]

[0083] Synthesis Example 3 The compound represented by the following chemical formula 3a is obtained in the same manner as in Synthesis Example 1, except that a 1M THF solution of 1-propene-2-magnesium bromide (62.3 mmol) is used instead of tert-butyl magnesium bromide. [ka]

[0084] (Synthesis of the second organometallic compound) Synthesis Example 4 The compound represented by the following chemical formula 1b is obtained in the same manner as in Synthesis Example 1, except that a 1M THF solution of cyclopentyl magnesium bromide (62.3 mmol) is used instead of tert-butyl magnesium bromide. [ka]

[0085] Synthesis Example 5 Dissolve Ph3SnCl (20 g, 51.9 mmol) in 100 mL of anhydrous tetrahydrofuran (THF) in a 250 mL two-neck round-bottom flask and cool to 0 °C using an ice bath. Then, slowly add cyclohexylmagnesium bromide 1 M THF solution (62.3 mmol). After the addition is complete, stir at 25 °C for 12 hours. After vacuum distillation, dissolve in 50 mL of CHCl and add 3 equivalents (155.7 mmol) of 2 M HCl diethyl ether solution slowly at -78 °C for 30 minutes. After stirring at 25 °C for 12 hours, concentrate the solvent, vacuum distill, and then dissolve again in 50 mL of CHCl and add 3 equivalents (51.9 mmol) of silver tert-butoxide dropwise at 0 °C. Remove the resulting solid by filtration. Distill the filtrate to obtain the compound represented by formula 2b. [ka]

[0086] Synthesis Example 6 Dissolve Sn(NEt2)4 (20 g, 49.1 mmol) in 100 mL of anhydrous tetrahydrofuran (THF) in a 250 mL two-neck round-bottom flask and cool to -50°C using an ice bath. Then, slowly add 1 M phenyllithium THF solution (10.0 mmol). After the addition is complete, stir at 25°C for 12 hours. Add excess isopropanol (100 mmol) at -50°C and gradually warm to room temperature. Remove the solvent by distillation under reduced pressure, and isolate and purify the remaining material under reduced pressure to obtain phenytin triisofurooxide (PhSn(OiPr)3). Add 50 mL of anhydrous toluene, slowly add isobutyric acid at -20°C, and then heat to reflux for 2 hours. Then, vacuum distill to obtain the compound represented by formula 3b. [ka]

[0087] Synthesis Example 7 Dissolve Sn(NEt2)4 (20 g, 49.1 mmol) in 100 mL of anhydrous tetrahydrofuran (THF) in a 250 mL two-neck round-bottom flask and cool to -50°C using an ice bath. Then, slowly add 1 M pyridine magnesium bromide in THF (10.0 mmol). After the addition is complete, stir at 25°C for 12 hours. Add excess isopropanol (100 mmol) at -50°C and slowly warm to room temperature. Remove the solvent by distillation under reduced pressure, and separate and purify the remaining material under reduced pressure to obtain pyridinetin triisofurooxide (PySn(OiPr)3). Add 50 mL of anhydrous toluene, slowly add isobutyric acid at -20°C, and then heat to reflux for 2 hours. Then, vacuum distill to obtain the compound represented by formula 4b. [ka]

[0088] (Production of semiconductor photoresist composition) Examples 1 to 14 and Comparative Examples 1 to 7 The compounds represented by Chemical Formula 1a, Chemical Formula 2a, Chemical Formula 3a, Chemical Formula 1b, Chemical Formula 2b, Chemical Formula 3b, and Chemical Formula 4b obtained in Synthesis Examples 1 to 7 were each dissolved in PGMEA (propylene glycol monomethyl ether acetate) at a concentration of 3 wt %, and filtered through a 0.1 μm PTFE syringe filter to prepare photoresist compositions.

[0089] Evaluation 1: Coating surface roughness evaluation The photoresist compositions of Examples 1 to 14 and Comparative Examples 1 to 7 were coated onto wafers, and then exposed to 100°C on a hot plate for 60 seconds. The surface roughness (Rq) was measured using an atomic force microscope (AFM). The results were evaluated according to the following criteria and are shown in Table 1.

[0090] [Surface roughness (Rq value)] -○: 0.4 or less, -△: More than 0.4 but less than 0.7, -X:0.7 exceeded

[0091] Evaluation 2: Line Edge Roughness (LER) evaluation A linear array of 50 circular pads, each 500 μm in diameter, was projected using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET) onto wafers coated with the photoresist compositions of Examples 1 to 14 and Comparative Examples 1 to 7. Pad exposure time was adjusted so that an increased EUV dose was applied to each pad.

[0092] The resist and substrate were then post-exposure baked (PEB) on a hotplate at 160 °C for 120 seconds. The baked film was then immersed in a developer (2-heptanone) for 30 seconds each, followed by a further 10-second wash in the same developer to create a negative-tone image, i.e., remove the unexposed coating. A final hotplate bake at 150 °C for 2 minutes completed the process.

[0093] The line edge roughness (LER) of the line and space pattern was measured using an electron microscope. The results were evaluated according to the following criteria and are shown in Table 1.

[0094] Line Edge Roughness (LER) -○: 4nm or less, -△: More than 4nm and less than 7nm, -X: Exceeding 7nm

[0095] [Table 1]

[0096] From the results in Table 1, it can be seen that the semiconductor photoresist compositions according to the examples have reduced surface roughness, excellent coating properties, and excellent line edge roughness compared to the comparative examples.

[0097] While 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 are possible 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]

[0098] 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. A first organometallic compound represented by the following chemical formula 1: a second organometallic compound represented by the following formula 2: A composition for semiconductor photoresist, comprising a solvent: 【Chemical 1】 【Chemistry 2】 In the above Chemical Formula 1 and Chemical Formula 2, M １ and M ２ are each independently Sn or Te, R １ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, or -L ａ -O-R ａ (Here, L ａ is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, and R ａ is a substituted or unsubstituted C1-C20 alkyl group; R ２ is a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group; X １ and X ２ are each independently selected from alkoxy and aryloxy (—OR ｂ , where R ｂ 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, a substituted or unsubstituted C7 to C30 arylalkyl group, or a combination thereof; a carboxyl group (—O(CO)R ｃ , R ｃ 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, a substituted or unsubstituted C7 to C30 arylalkyl group, or a combination thereof), alkylamide or dialkylamide (—NR ｄ R ｅ , where R ｄ and R ｅ 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, a substituted or unsubstituted C7 to C30 arylalkyl group, or a combination thereof), amidato (—NR ｆ (COR ｇ ), where R ｆ and R ｇ 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, a substituted or unsubstituted C7 to C30 arylalkyl group, or a combination thereof), amidinato (—NR ｈ C (NR ｉ ) R ｊ , where R ｈ , R ｉ and R ｊ 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, a substituted or unsubstituted C7 to C30 arylalkyl group, or a combination thereof), alkylthio and arylthio (-SR ｋ , where R ｋ 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, a substituted or unsubstituted C7 to C30 arylalkyl group, or a combination thereof), and a thiocarboxyl group (—S(CO)R ｌ , R ｌ is selected from hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, or a combination thereof; a, b, c, and d are each independently an integer from 1 to 5; a+b is an integer of 4 or 6, c+d is an integer of 4 or 6.

2. 2. The semiconductor photoresist composition according to claim 1, wherein the first organometallic compound and the second organometallic compound are contained in a weight ratio of 90:10 to 40:

60.

3. 2. The semiconductor photoresist composition according to claim 1, wherein the first organometallic compound and the second organometallic compound are contained in a weight ratio of 80:20 to 40:

60.

4. The R １ is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, or -L ａ -O-R ａ (Here, L ａ is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, R ａ is a substituted or unsubstituted C1-C20 alkyl group; The R ２ is a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group; X １ and X ２ are each independently selected from alkoxy and aryloxy (—OR ｂ , where R ｂ is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 arylalkyl group, or a combination thereof; a carboxyl group (—O(CO)R ｃ , R ｃ is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 arylalkyl group, or a combination thereof), alkylamide or dialkylamide (—NR ｄ R ｅ , where R ｄ and R ｅ are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 arylalkyl group, or a combination thereof), amidato (—NR ｆ (COR ｇ ), where R ｆ and R ｇ are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 arylalkyl group, or a combination thereof), or amidinato (—NR ｈ C (NR ｉ ) R ｊ , where R ｈ , R ｉ and R ｊ are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 arylalkyl group, or a combination thereof), alkylthio and arylthio (-SR ｋ , where R ｋ is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 arylalkyl group, or a combination thereof), and a thiocarboxyl group (—S(CO)R ｌ , R ｌ is selected from hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 arylalkyl group, or a combination thereof.

5. The R １ 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 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 ２ is 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 phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted xylene group, a substituted or unsubstituted pyridine group, a substituted or unsubstituted pyrrolidine group, a substituted or unsubstituted piperidine group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted tetrahydrofuranyl group, a substituted or unsubstituted pyranyl group, a substituted or unsubstituted tetrahydropyranyl group, a substituted or unsubstituted dioxane, a substituted or unsubstituted morpholine group, or a combination thereof; The R ｂ 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; The R ｃ , R ｄ , R ｅ , R ｆ , R ｇ , R ｈ , R ｉ , R ｊ , R ｋ , and R ｌ 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 substituted benzyl group, or a combination thereof.

6. 2. The semiconductor photoresist composition of claim 1, wherein the second organometallic compound is one selected from the compounds listed in Group 2 below: 【Chemistry 3】 【Chemistry 4】

7. 2. The semiconductor photoresist composition of claim 1, wherein the first organometallic compound is one selected from the compounds listed in Group 1 below: 【Chemistry 5】

8. 2. The semiconductor photoresist composition according to claim 1, wherein the first organometallic compound and the second organometallic compound are contained in an amount of 1 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, an inhibitor, and combinations thereof.

10. forming a film to be etched on a substrate; Applying the semiconductor photoresist composition according to any one of claims 1 to 9 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.

11. 11. The pattern formation method according to claim 10, wherein the step of forming the photoresist pattern uses light with a wavelength of 5 nm to 150 nm.

12. The pattern formation method according to claim 10, further comprising the step of providing a resist underlayer film formed between the substrate and the photoresist film.

13. 11. The pattern forming method according to claim 10, wherein the photoresist pattern has a width of 5 nm to 100 nm.

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