Semiconductor photoresist composition and pattern forming method using the same

Abstract

To provide a semiconductor photoresist composition exhibiting excellent sensitivity and improved stability and coatability, and a pattern forming method using the same.SOLUTION: The present invention relates to a semiconductor photoresist composition comprising an organometallic compound represented by Chemical Formula 1, and a solvent, and a pattern forming method 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] One embodiment of the present invention provides a semiconductor photoresist composition that exhibits excellent sensitivity, and has improved stability and coatability.

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

[0012] A composition for semiconductor photoresist according to one embodiment of the present invention includes an organometallic compound represented by the following Chemical Formula 1 and a solvent.

[0013] [ka]

[0014] In the above Chemical Formula 1, A is a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or a combination thereof; L 1represents a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, X 1 ~X 3 are each independently selected from alkoxy and aryloxy (-OR b , where R b 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, or a combination thereof), a carboxyl group (-O(CO)R c , R c 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, 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 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, or a combination thereof), amidato (-NR f (COR g ), where R f and R gare 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, 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 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, or a combination thereof), alkylthio and arylthio (-SR k , where R k 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, or a combination thereof) and a thiocarboxyl group (-S(CO)R l , R l 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, or a combination thereof; X 1 ~X 3 At least one of the groups is a carboxyl group (-O(CO)Rc , R c 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, or a combination thereof).

[0015] A method for forming a pattern according to another embodiment of the present invention includes 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; patterning the photoresist layer to form a photoresist pattern; and etching the layer to be etched using the photoresist pattern as an etching mask. [Effects of the Invention]

[0016] A composition for semiconductor photoresist according to one embodiment of the present invention can provide a photoresist pattern with improved storage stability, coating properties, and sensitivity. [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, in which: 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, a carbonyl 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, "Unsubstituted" means substituted with 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, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, or a combination thereof. "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 10 carbon atoms. For example, the alkyl group may be an alkyl group having 1 to 8 carbon atoms, 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 10 carbon atoms, such as a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, or a cycloalkyl group having 3 to 6 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, the term "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.

[0027] 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.

[0028] 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.

[0029] In the chemical formulas described herein, t-Bu refers to a tert-butyl group.

[0030] As used herein, the term "heterocyclic group" includes not only aromatic rings such as "heteroaryl groups" but also non-aromatic rings, and unless otherwise specified, refers to a ring having 2 to 60 carbon atoms and containing one or more heteroatoms, but is not limited thereto. Unless otherwise specified, "heteroatom" refers to an element other than carbon, such as N, O, S, P, or Si, and may contain heteroatom groups such as SO2 and P=O in place of carbon atoms forming the ring. As used herein, heterocyclic groups include monocyclic rings, ring aggregates, linked multiple ring systems, spiro compounds, etc., containing heteroatoms.

[0031] Hereinafter, a semiconductor photoresist composition according to one embodiment will be described.

[0032] A composition for semiconductor photoresist according to one embodiment of the present invention includes an organometallic compound represented by the following Chemical Formula 1 and a solvent.

[0033] [ka]

[0034] In the above Chemical Formula 1, A is a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or a combination thereof; L 1represents a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, X 1 ~X 3 are each independently selected from alkoxy and aryloxy (-OR b , where R b 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, or a combination thereof), a carboxyl group (-O(CO)R c , R c 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, 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 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, or a combination thereof), amidato (-NR f (COR g ), where R f and R gare 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, 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 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, or a combination thereof), alkylthio and arylthio (-SR k , where R k 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, or a combination thereof) and a thiocarboxyl group (-S(CO)R l , R l 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, or a combination thereof; X 1 ~X 3 At least one of the groups is a carboxyl group (-O(CO)Rc , R c 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, or a combination thereof).

[0035] When an organometallic compound having a cyclic substituent is used as in the present invention, the thermal stability of the thin film during coating is high and crystal formation is suppressed, thereby improving coatability.

[0036] As an example, the X 1 ~X 3 are each independently selected from alkoxy and aryloxy (-OR b , where R b 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, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, or a combination thereof), a carboxyl group (-O(CO)R c , R c 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, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, or a combination thereof), alkylamide or dialkylamide (-NR d R e , where R d and R eare 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, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, or a combination thereof), amidato (-NR f (COR g ), where R f and R g 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, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, 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 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, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, or a combination thereof), alkylthio and arylthio (-SR k , where R k 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, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, or a combination thereof) and a thiocarboxyl group (-S(CO)R l , Rl is 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, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, or a combination thereof; X 1 ~X 3 At least one of the groups is a carboxyl group (-O(CO)R c , R c may be 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, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, or a combination thereof.

[0037] As a specific example, the X 1 ~X 3 are carboxyl groups (-O(CO)R c , R c may be 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, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, or a combination thereof.

[0038] In one embodiment, the R bis 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 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 unsubstituted benzyl group, or a combination thereof.

[0039] On the other hand, A and L 1 At least one of the groups may contain an unsaturated bond.

[0040] When the organometallic compound contains such an unsaturated bond, it is able to be solubility in an organic solvent. Therefore, the organometallic compound according to one embodiment has relatively excellent solubility in an organic solvent and storage stability, and can easily form a pattern even in a low concentration developer.

[0041] Furthermore, since the bond dissociation energy between the central metal atom and carbon with extreme ultraviolet light can be reduced, a semiconductor resist composition containing the organometallic compound exhibits excellent sensitivity, and when a pattern is formed using the compound, a pattern that does not collapse even if it has a high aspect ratio can be formed.

[0042] For example, A may contain an unsaturated bond, and A may be, for example, a substituted or unsubstituted cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

[0043] As a specific example, A may be a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 20 carbon atoms.

[0044] For example, A is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and L 1 may be a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms.

[0045] When A is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, L 1When is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, excellent sensitivity can be exhibited by lowering the bond dissociation energy of the carbon bonded to the central metal atom with extreme ultraviolet light.

[0046] For example, A may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted indanyl group, a substituted or unsubstituted tetralin 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 cycloheptyl group, a substituted or unsubstituted cyclooctyl group, a substituted or unsubstituted cyclononyl group, a substituted or unsubstituted cyclopentenyl group, a substituted or unsubstituted cyclohexenyl group, a substituted or unsubstituted cycloheptenyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclopentenyl group, a substituted or unsubstituted cyclohexenyl group, a substituted or unsubstituted cycloheptenyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclopentenyl group, a substituted or unsubstituted cyclohexenyl group, a substituted or unsubstituted cyclooctyl group, a substituted or unsubstituted cyclononyl group, a substituted or unsubstituted cyclopentenyl group, a substituted or unsubstituted cyclohexenyl group, a substituted or unsubstituted cycloheptenyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexen ... or unsubstituted bicyclo[2,2,1]heptyl group, substituted or unsubstituted bicyclo[2,2,1]heptenyl group, substituted or unsubstituted bicyclo[2,2,1]octyl group, substituted or unsubstituted bicyclo[2,2,4]octyl group, substituted or unsubstituted tricyclo[3,3,1,1]decyl group, substituted or unsubstituted bicyclo[4,3,0]nonyl group, substituted or unsubstituted bicyclo[4,4,0]octyl group, substituted or unsubstituted pyrrolidinyl group, substituted or unsubstituted oxolanyl group, substituted or unsubstituted tetrahydrothiophenyl group group), a substituted or unsubstituted pyrrole group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted piperidinyl group, a substituted or unsubstituted oxanyl group, a substituted or unsubstituted tetrahydrothiopyranyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyranyl group, or a substituted or unsubstituted thiopyranyl group.

[0047] The organometallic compound can be selected from the compounds listed in Group 1 below.

[0048] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0049] The organometallic compound strongly absorbs extreme ultraviolet light at 13.5 nm and has excellent sensitivity to light having high energy.

[0050] In one embodiment, the semiconductor photoresist composition may contain the organometallic compound in an amount of, but not limited to, 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 %, or for example, 1 wt % to 5 wt %, based on 100 wt % of the semiconductor photoresist composition. When the organometallic compound 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.

[0051] The semiconductor photoresist composition according to one embodiment of the present invention includes the organometallic compound, thereby providing a semiconductor photoresist composition having excellent sensitivity and pattern formability.

[0052] The solvent contained in the semiconductor resist 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.

[0053] In one embodiment, the semiconductor resist composition may further include a resin in addition to the organometallic compound and the solvent.

[0054] The resin may be a phenolic resin containing at least one aromatic moiety listed in Group 2 below.

[0055] [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 one embodiment preferably comprises the organometallic compound, a solvent, and a resin. However, the semiconductor photoresist composition according to the above embodiment may further include additives, such as surfactants, crosslinkers, leveling agents, organic acids, quenchers, or combinations thereof.

[0060] The surfactant may be, for example, but not limited to, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, or a combination thereof.

[0061] 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.

[0062] The leveling agent is used to improve coating flatness during printing, and any known leveling agent that is commercially available can be used.

[0063] 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.

[0064] The quencher can be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0065] The amount of these additives used can be easily adjusted depending on the desired physical properties, and they may also be omitted.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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; patterning the photoresist layer to form a photoresist pattern; and etching the layer to be etched using the photoresist pattern as an etching mask.

[0070] 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.

[0071] 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.

[0072] 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, the present invention 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] The semiconductor photoresist composition has already been explained in detail, so a duplicate explanation will be omitted.

[0079] 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.

[0080] Referring to FIG. 1( c ), the photoresist film 106 is selectively exposed to light using a patterned mask 110 .

[0081] 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).

[0082] More specifically, the exposure light in 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).

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] Next, 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.

[0091] 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.

[0092] The thin film 102 can be etched by dry etching using an etching gas, such as CHF3, CF4, Cl2, BCl3, or a mixture thereof.

[0093] 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]

[0094] 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.

[0095] (Synthesis of organometallic compounds) Synthesis Example 1 30 g of tetrakisdiethylaminotin was placed in a 250 mL Schlenk flask, and 74 mL of anhydrous normal hexane was added, followed by stirring at −20° C. in a nitrogen atmosphere.

[0096] To this was slowly added 40.5 mL of a 2.0 M solution of cyclopentyl magnesium bromide in diethyl ether at -20°C for 1 hour, and then the temperature was raised to room temperature and the solution was stirred at room temperature for 6 hours. The reaction solution was filtered under anhydrous nitrogen atmosphere to remove the formed solid, and the filtrate was concentrated under reduced pressure to obtain the compound represented by M-1 below. [ka]

[0097] Then, 50 g of the compound represented by M-1 was placed in a 500 mL Schlenk flask, and 124 mL of anhydrous toluene was added, followed by stirring at −10° C. in a nitrogen atmosphere.

[0098] 23 g of acetic anhydride was slowly added thereto at -10°C, and the temperature was raised to room temperature, and the solution was stirred for 1 hour. The reaction solution was concentrated under reduced pressure to finally obtain the compound represented by P-1 below. [ka]

[0099] Synthesis Example 2 30 g of tetrakisdiethylaminotin was placed in a 250 mL Schlenk flask, and 74 mL of anhydrous normal hexane was added, followed by stirring at −20° C. in a nitrogen atmosphere.

[0100] To this was slowly added 40.5 mL of a 2.0 M solution of cyclohexyl magnesium bromide in diethyl ether at -20°C for 1 hour, and then the temperature was raised to room temperature and the solution was stirred at room temperature for 6 hours. The reaction solution was filtered under anhydrous nitrogen atmosphere to remove the formed solid, and the filtrate was concentrated under reduced pressure to obtain the compound represented by M-2 below.

[0101] Then, 50 g of the compound represented by M-2 was placed in a 500 mL Schlenk flask, and 120 mL of anhydrous toluene was added, followed by stirring at −10° C. in a nitrogen atmosphere.

[0102] 27.4 g of propionic anhydride was slowly added thereto at -10°C, and the temperature was raised to room temperature, and the solution was stirred at room temperature for 1 hour. The reaction solution was concentrated under reduced pressure to finally obtain the compound represented by P-2 below. [ka]

[0103] Synthesis Example 3 The compound represented by P-3 below was obtained in the same manner as in Synthesis Example 2, except that cyclopentanemethylmagnesium bromide diethyl ether was used instead of cyclohexylmagnesium bromide diethyl ether. [ka]

[0104] Synthesis Example 4 The compound represented by P-4 below was obtained in the same manner as in Synthesis Example 2, except that benzylmagnesium bromide diethyl ether was used instead of cyclohexylmagnesium bromide diethyl ether. [ka]

[0105] Synthesis Example 5 The compound represented by P-5 below was obtained in the same manner as in Synthesis Example 1, except that 3-methylbenzylmagnesium bromide diethyl ether was used instead of cyclopentylmagnesium bromide diethyl ether. [ka]

[0106] Synthesis Example 6 The compound represented by the following P-6 was obtained in the same manner as in Synthesis Example 2, except that 1-bicyclo[2.2.2]octylmagnesium bromide tetrahydrofuran was used instead of cyclohexylmagnesium bromide diethyl ether. [ka]

[0107] Synthesis Example 7 The compound represented by P-7 below was obtained in the same manner as in Synthesis Example 2 above, except that exo-2-norbornylmagnesium bromide diethyl ether was used instead of cyclohexylmagnesium bromide diethyl ether. [ka]

[0108] Synthesis Example 8 The compound represented by P-8 below was obtained in the same manner as in Synthesis Example 1, except that 1-adamantyl magnesium bromide tetrahydrofuran was used instead of cyclopentyl magnesium bromide diethyl ether. [ka]

[0109] Synthesis Example 9 The compound represented by P-9 below was obtained in the same manner as in Synthesis Example 1, except that 3-cyclohexenylmagnesium bromide diethyl ether was used instead of cyclopentylmagnesium bromide diethyl ether. [ka]

[0110] Synthesis Example 10 A compound represented by the following P-10 was obtained in the same manner as in Synthesis Example 1, except that 3-thiopenemethylmagnesium bromide diethyl ether was used instead of cyclopentylmagnesium bromide diethyl ether. [ka]

[0111] Comparative synthesis example 1 A compound represented by the following formula P-11 was obtained in the same manner as in Synthesis Example 1, except that normal butyl magnesium bromide diethyl ether was used instead of cyclopentyl magnesium bromide diethyl ether. [ka]

[0112] Comparative synthesis example 2 A compound represented by the following formula P-12 was obtained in the same manner as in Synthesis Example 1, except that normal butyl magnesium bromide diethyl ether was used instead of cyclopentyl magnesium bromide diethyl ether and absolute ethanol was used instead of acetic acid. [ka]

[0113] (Production of semiconductor photoresist composition) Examples 1 to 10, Comparative Examples 1 and 2 The compounds obtained in Synthesis Examples 1 to 10 and the compounds obtained in Comparative Synthesis Examples 1 and 2 were each dissolved in PGMEA (propylene glycol monomethyl ether acetate) at 3 wt % and filtered through a 0.1 μm PTFE syringe filter to prepare photoresist compositions.

[0114] Evaluation 1: Sensitivity 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 10 and Comparative Examples 1 and 2. Pad exposure time was adjusted so that an increased EUV dose was applied to each pad.

[0115] The resist and substrate were then post-exposure baked (PEB) on a hot plate at 160°C for 120 seconds. The baked film was then immersed in a developer (2-heptanone) for 30 seconds each, and then washed in the same developer for an additional 10 seconds to form a negative tone image, i.e., remove the unexposed coating. The process was terminated by a final hot plate bake at 150°C for 2 minutes.

[0116] 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. Dg (energy level at which development is complete) was evaluated for each type of resist according to the following criteria, as shown in Table 1.

[0117] *Evaluation criteria (Dg value) A: 16 mJ / cm 2 less than B: 16 mJ / cm 2 More than ~23mJ / cm 2 less than C: 23 mJ / cm 2 More than ~30mJ / cm 2 less than D: 30 mJ / cm 2 End

[0118] Evaluation 2: Evaluation of storage stability The storage stability of the organometallic compounds used in Examples 1 to 10 and Comparative Examples 1 and 2 was evaluated according to the following criteria, and the results are shown in Table 1 below.

[0119] [Storage stability] The semiconductor photoresist compositions according to Examples 1 to 10 and Comparative Example 1 were left at room temperature (20±5° C.) for a specific period of time, and the degree of precipitation was observed with the naked eye and evaluated according to the following storage standards.

[0120] *Evaluation criteria -○: Can be stored for more than 2 months -△: Can be stored for 2 weeks or more but less than 2 months -X: Can be stored for less than 2 weeks

[0121] [Table 1]

[0122] From the results in Table 1, it can be seen that the semiconductor photoresist compositions according to the Examples have superior sensitivity and significantly improved storage stability compared to the Comparative Examples.

[0123] 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]

[0124] 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 represented by the following chemical formula 1: A composition for semiconductor photoresist, comprising a solvent: 【Chemical 1】 In the above Chemical Formula 1, A is a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or a combination thereof; L １ represents a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, X １ ~X ３ are each independently selected from alkoxy and aryloxy (—OR ｂ , where R ｂ 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, or a combination thereof; a carboxyl group (—O(CO)R ｃ , R ｃ 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, 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 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, or a combination thereof), amidato (—NR ｆ (COR ｇ ), where R ｆ and R ｇ 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, 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 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, or a combination thereof), alkylthio and arylthio (-SR ｋ , where R ｋ 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, or a combination thereof), and a thiocarboxyl group (—S(CO)R ｌ , R ｌ 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, or a combination thereof; X １ ~X ３ At least one of the groups is a carboxyl group (—O(CO)R ｃ , R ｃ 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, or a combination thereof).

2. The X １ ~X ３ are each independently selected from alkoxy and aryloxy (—OR ｂ , where R ｂ 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, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, or a combination thereof; a carboxyl group (—O(CO)R ｃ , R ｃ 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, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, 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 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, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, or a combination thereof), amidato (—NR ｆ (COR ｇ ), where R ｆ and R ｇ 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, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, 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 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, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, or a combination thereof), alkylthio and arylthio (-SR ｋ , where R ｋ 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, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, or a combination thereof), and a thiocarboxyl group (—S(CO)R ｌ , R ｌ is 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, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, or a combination thereof; The X １ ~X ３ At least one of the groups is a carboxyl group (—O(CO)R ｃ , R ｃ 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, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, or a combination thereof.

3. 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 unsubstituted benzyl group, or a combination thereof.

4. The A and the L １ 2. The semiconductor photoresist composition according to claim 1, wherein at least one of the groups contains an unsaturated bond.

5. 2. The semiconductor photoresist composition according to claim 1, wherein A is a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 20 carbon atoms, or a combination thereof.

6. A is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, L １ 2. The semiconductor photoresist composition according to claim 1, wherein is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms.

7. A is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted indanyl group, a substituted or unsubstituted tetralin 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 cycloheptyl group, a substituted or unsubstituted cyclooctyl group, a substituted or unsubstituted cyclononyl group, a substituted or unsubstituted cyclopentenyl group, a substituted or unsubstituted cyclohexenyl group, a substituted or unsubstituted cycloheptenyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexenyl group, a substituted or unsubstituted cyclooctyl group, a substituted or unsubstituted cyclononyl group, a substituted or unsubstituted cyclopentenyl group, a substituted or unsubstituted cyclohexenyl group, a substituted or unsubstituted cycloheptenyl group, a substituted or unsubstituted cyclopentenyl group, a substituted or unsubstituted cyclohexenyl group, a substituted or unsubstituted cyclooctyl group, a substituted or unsubstituted cyclononyl group, a substituted or unsubstituted cyclopentenyl group, a substituted or unsubstituted cyclohexenyl group, a substituted or unsubstituted cyclohexenyl group, a substituted or unsubstituted cyclohexenyl group, a substituted or unsubstituted cyclohexenyl group, a substituted or unsubstituted cyclooctyl group, a substituted or unsubstituted cyclopentenyl group, a substituted or unsubstituted cyclohex ... is an unsubstituted bicyclo[2,2,1]heptyl group, a substituted or unsubstituted bicyclo[2,2,1]heptenyl group, a substituted or unsubstituted bicyclo[2,2,1]octyl group, a substituted or unsubstituted bicyclo[2,2,4]octyl group, a substituted or unsubstituted tricyclo[3,3,1,1]decyl group, a substituted or unsubstituted bicyclo[4,3,0]nonyl group, a substituted or unsubstituted bicyclo[4,4,0]octyl group, a substituted or unsubstituted pyrrolidinyl group, a substituted or unsubstituted oxolanyl group, a substituted or unsubstituted tetrahydrothiophenyl group, 2. The semiconductor photoresist composition according to claim 1, wherein the substituted or unsubstituted aryl group is a substituted or unsubstituted aryl group, ...

8. 2. The semiconductor photoresist composition according to claim 1, wherein the organometallic compound is one selected from the compounds listed in Group 1 below: 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】

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

10. 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.

11. forming a film to be etched on a substrate; applying the semiconductor photoresist composition according to any one of claims 1 to 10 onto the film to be etched to form a photoresist film; patterning the photoresist film to form a photoresist pattern; and etching the target layer using the photoresist pattern as an etching mask.

12. 12. The method of claim 11, wherein the step of forming the photoresist pattern uses light having a wavelength of 5 nm to 150 nm.

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

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