Semiconductor photoresist composition and method of forming pattern using the same

Abstract

To provide a composition for a semiconductor photoresist having improved coating properties and storage stability while maintaining excellent sensitivity characteristics, and a pattern forming method using the same.SOLUTION: The semiconductor photoresist composition contains an organometallic compound, a chain carboxylic acid compound containing at least one carboxyl group, a cyclic carboxylic acid compound expressed by chemical formula 1, and a solvent, and the pattern forming method uses the composition. Details of Chemical Formula 1 are as described in the specification.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 iodine 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 performing at spatial resolutions of 16 nm or less. Currently, traditional chemically amplified (CA) photoresists struggle to meet specifications for resolution, photo speed, feature roughness, and line edge roughness (LER) for next-generation devices.

[0004] Intrinsic image blur, resulting from acid-catalyzed reactions in these polymeric photoresists, limits resolution at small feature sizes and has long been 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 also be challenged by roughness issues at small feature sizes, and experiments have shown that line edge roughness (LER) increases as the photo speed 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 a new class of high-performance photoresists.

[0006] To overcome the drawbacks of chemically amplified organic photosensitive compositions, 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 known to be less susceptible to the stochastic effect, resulting in reduced 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. Ochiji, 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 light speed 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] Recently, tin-containing molecules have been recognized as having excellent extreme ultraviolet absorption, and active research has been conducted on them. In the case of organotin polymers, alkyl ligands are dissociated by light absorption or the secondary electrons generated by the absorption, and crosslinking with peripheral chains through iodine bonds enables negative-tone patterning that is resistant to removal by organic developers. While these organotin polymers have demonstrated dramatic improvements in sensitivity while maintaining resolution and line edge roughness, further improvements in their patterning properties are required for commercialization. Summary of the Invention [Problem to be solved by the invention]

[0010] One embodiment provides a semiconductor photoresist composition that has improved coating properties and storage stability while maintaining excellent sensitivity characteristics.

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

[0012] A semiconductor photoresist composition according to one embodiment includes an organometallic compound, a chain carboxylic acid compound having at least one carboxyl group, a cyclic carboxylic acid compound represented by the following Chemical Formula 1, and a solvent. [ka]

[0013] In the above Chemical Formula 1, 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, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group; n1 is the number of substituents substituted on A, from one to the maximum; Ring A is a substituted or unsubstituted C3 to C20 non-aromatic carbocyclic group or a substituted or unsubstituted C6 to C30 aromatic carbocyclic group; m1 is an integer of 1 to 3.

[0014] 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.

[0015] In one embodiment, the semiconductor photoresist composition can provide a photoresist pattern that has improved coating properties, reduced surface roughness, improved stability in solution, and the same performance in sensitivity, LER, and pattern linewidth as a given group. [Brief explanation of the drawings]

[0016] [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

[0017] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings, but in this description, descriptions of well-known functions or configurations will be omitted in order to clarify the gist of the description.

[0018] In order to clearly explain this description, parts that are 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 this description is not necessarily limited to those shown in the drawings.

[0019] 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.

[0020] 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 , 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, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, a C1 to C30 alkyl group, a C1 to C10 haloalkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a C1 to C20 sulfide group, or a combination thereof. "Unsubstituted" means that the hydrogen atom remains as a hydrogen atom without being replaced by another substituent.

[0021] 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.

[0022] The alkyl group may be a C1 to C8 alkyl group. For example, the alkyl group may be a C1 to C7 alkyl group, a C1 to C6 alkyl group, or a C1 to C5 alkyl group. For example, the C1 to C5 alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or a 2,2-dimethylpropyl group.

[0023] In this description, unless otherwise defined, the term "cycloalkyl group" refers to a monovalent cyclic aliphatic saturated hydrocarbon group.

[0024] The cycloalkyl group may be a C3 to C8 cycloalkyl group, such as a C3 to C7 cycloalkyl group, a C3 to C6 cycloalkyl group, a C3 to C5 cycloalkyl group, or a C3 to C4 cycloalkyl group. For example, the cycloalkyl group may be, but is not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

[0025] As used herein, the term "aryl group" refers to a substituent in which all elements of the cyclic substituent 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.

[0026] As used herein, the term "heteroaryl group" refers to an aryl group containing at least one heteroatom selected from the group consisting of N, O, S, P, and Si. Two or more heteroaryl groups may be directly linked via a sigma bond, or when the heteroaryl group contains two or more rings, the two or more rings may be fused to each other. When the heteroaryl group is a fused ring, each ring may contain 1 to 3 heteroatoms.

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

[0030] A composition for semiconductor photoresist according to one embodiment of the present invention may include an organometallic compound, a chain carboxylic acid compound, a cyclic carboxylic acid compound represented by Chemical Formula 1, and a solvent.

[0031] The semiconductor photoresist composition according to the present invention is a composition comprising an organometallic compound, two carboxylic acid compounds, and a solvent. By including both a chain carboxylic acid compound and a substituted cyclic carboxylic acid compound, the sensitivity of a pattern formed using the composition to extreme ultraviolet light can be increased, and pattern roughness can be improved.

[0032] The cyclic carboxylic acid compound is represented by the following chemical formula 1. [ka]

[0033] In the above Chemical Formula 1, R 1is 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, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group; n1 is the number of substituents substituted on A, from one to the maximum; Ring A is a substituted or unsubstituted C3 to C20 non-aromatic carbocyclic group or a substituted or unsubstituted C6 to C30 aromatic carbocyclic group; m1 is an integer of 1 to 3.

[0034] In this specification, a C3-C20 non-aromatic carbocyclic group refers to a saturated or unsaturated cyclic group having 3 to 20 carbon atoms as ring-forming atoms. The C3-C20 non-aromatic carboxyl group may be a monocyclic group or a polycyclic group.

[0035] In this specification, the C6 to C30 aromatic carboxyl group refers to an aromatic ring having 6 to 20 carbon atoms as ring-forming atoms, and can be selected from, for example, a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, and a chrysene group, but is not limited thereto.

[0036] The non-aromatic carboxyl group and the aromatic carboxyl group may be variously modified, such as a divalent group, a trivalent group, or a tetravalent group, depending on the number of linked substituents.

[0037] As an example, the ring A may be a substituted or unsubstituted cyclopentane group, a substituted or unsubstituted cyclohexane group, a substituted or unsubstituted heptane group, a substituted or unsubstituted octane group, a substituted or unsubstituted cyclopentene group, a substituted or unsubstituted cyclohexene group, a substituted or unsubstituted benzene group, a substituted or unsubstituted naphthalene group, a substituted or unsubstituted anthracene group, a substituted or unsubstituted phenanthrene group, a substituted or unsubstituted pyrene group, a substituted or unsubstituted triphenylene group, or a combination thereof.

[0038] For example, the cyclic carboxylic acid compound is represented by the following Chemical Formula 1A or Chemical Formula 1B. [ka]

[0039] In the above Chemical Formula 1A or Chemical Formula 1B, R 4 ~R 19 are each independently a hydrogen atom, 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, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group; R 4 ~R 14 at least one of the 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, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group; R 15 ~R 19At least one of the groups 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, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group.

[0040] In one embodiment, the R 4 ~R 14 at least one of is a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted pentyl group, or a combination thereof; R 15 ~R 19 At least one of the may be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted pentyl group, or a combination thereof.

[0041] In a specific embodiment, the cyclic carboxylic acid compound may be selected from the compounds listed in Group 1 below. [ka]

[0042] Specifically, the chain carboxylic acid compound is represented by the following chemical formula 2. [ka]

[0043] In the above Chemical Formula 2, R2 and R 3 are each independently a hydrogen atom, a hydroxy group, a carboxyl group, 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, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group; L 1 and L 2 are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C3 to C20 cycloalkenylene group, or a substituted or unsubstituted C6 to C20 arylene group; n2 and n3 each independently represent an integer of 0 to 5, m2 and m3 are each independently an integer of 0 or 1; m2+m3 is an integer equal to or greater than 1, When n2 and n3 are each an integer of 2 or greater, each L 1 and L 2 are the same or different from each other.

[0044] When n2 is an integer equal to or greater than 2, each L 1 are the same or different from each other.

[0045] When n3 is an integer equal to or greater than 2, each L 2 are the same or different from each other.

[0046] m2 or m3 is 0-valent, L 1 or L 2 are R 2 and R 3and may be hydrogen, a hydroxy group, a carboxyl group, 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, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 aryl akyl group.

[0047] As an example, the above-mentioned R 2 and R 3 may each independently be hydrogen, a hydroxy group, 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, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C3 to C10 cycloalkenyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C7 to C20 arylalkyl group.

[0048] For example, the R 2 and R 3 may each independently be hydrogen, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted pentyl group, or a combination thereof.

[0049] As an example, the above L 1 and L 2 may each independently be a substituted or unsubstituted C1 to C7 alkylene group, a substituted or unsubstituted C2 to C10 alkenylene group, a substituted or unsubstituted C2 to C10 alkynylene group, a substituted or unsubstituted C3 to C10 cycloalkylene group, a substituted or unsubstituted C3 to C10 cycloalkenylene group, or a substituted or unsubstituted C6 to C12 arylene group.

[0050] For example, the L1 and L 2 may each independently be a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, a substituted or unsubstituted pentylene group, a substituted or unsubstituted cyclopentylene group, a substituted or unsubstituted cyclopentenylene group, a substituted or unsubstituted cyclopentadienylene group, or a substituted or unsubstituted cyclohexylene group.

[0051] In a specific embodiment, the chain carboxylic acid compound may be one selected from the compounds listed in Group 2 below. [ka]

[0052] The chain carboxylic acid compound and the cyclic carboxylic acid compound may be contained in a weight ratio of 9:1 to 1:9.

[0053] For example, they may be contained in a weight ratio of 9:1 to 2:8, 9:1 to 3:7, 8:2 to 3:7, or 8:2 to 5:5.

[0054] As a specific example, the chain carboxylic acid compound and the cyclic carboxylic acid compound may be contained in a weight ratio of 3:1 to 1:3 or 3:1 to 1:1.

[0055] The chain carboxylic acid compound and the cyclic carboxylic acid compound can be contained in an amount of 0.01 to 20% by weight relative to 100% by weight of the semiconductor photoresist composition.

[0056] For example, the chain carboxylic acid compound and the cyclic carboxylic acid compound can be contained in an amount of 0.01 to 10 wt %, 0.02 to 10 wt %, 0.03 to 10 wt %, or 0.05 to 10 wt % relative to 100 wt % of the semiconductor photoresist composition.

[0057] The organometallic compound may be contained in an amount of 0.5 to 30% by weight relative to 100% by weight of the composition for semiconductor photoresist.

[0058] When the composition for semiconductor photoresist according to one embodiment contains the chain carboxylic acid compound and the cyclic carboxylic acid compound within the above content ranges, the sensitivity of the photoresist can be improved.

[0059] The organometallic compound may be an organotin compound containing at least one of an organic oxy group and an organic carbonyloxy group.

[0060] For example, the organometallic compound is represented by the following chemical formula 3: [ka]

[0061] In the above Chemical Formula 3, R 20 is selected from a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, and a substituted or unsubstituted C7 to C30 arylalkyl group; R 21 ~R 23 are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, alkoxy, and aryloxy (-OR 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, or a combination thereof), a carboxyl group (-O(C=O)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, 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, 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, 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, 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, or a combination thereof) or a thiocarboxyl group (-SCO)R l , R l is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R 21 ~R 23 At least one of the groups is 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, or a combination thereof), a carboxyl group (-O(C=O)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, or a combination thereof), alkylamide or dialkylamide (-NR d R e , where R d and R eare each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), amidato (-NR 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, 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, 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, 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, or a combination thereof.

[0062] R 21 ~R 23 At least one of the groups is alkoxy and aryloxy (-OR b , where R a is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), and a carboxyl group (-O(C=O)R c , R c may be selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof.

[0063] Meanwhile, the compound represented by the formula 3 has -OR as a ligand. b or -O(C=O)R c By including the compound (I), a pattern formed using a semiconductor photoresist composition containing the compound can exhibit excellent limit resolution.

[0064] Also, -OR b or -O(C=O)R c The ligand can determine the solubility of the compound represented by Chemical Formula 3 in a solvent.

[0065] R 20 is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group containing one or more double or triple bonds, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C4 to C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof; R bis a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof; R c may be hydrogen, a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.

[0066] R 20 is a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propenyl group, a butenyl group, an ethanyl group, a propanyl group, a butanyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pentanoyl group, an ethoxy group, a propoxy group, or a combination thereof; R b is an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propenyl group, a butenyl group, an ethanyl group, a propanyl group, a butanyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, or a combination thereof; R c may be hydrogen, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, ethanyl, propanyl, butanyl, phenyl, tolyl, xylene, benzyl, or a combination thereof.

[0067] The organometallic compound is represented by the following chemical formula 4 or 5. [ka] In the above Chemical Formula 4, R 24 is a C1 to C31 hydrocarbyl group, where 0 <z≦2であり、0<(z+x)≦4であり; [ka] In the above Chemical Formula 5, R 25 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof; X is sulfur (S), selenium (Se), or tellurium (Te); Y is -OR m or -O(C=O)R n and R m is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R n is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; The a, b, c, and d are each independently an integer of 1 to 20.

[0068] The solvent included 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.

[0069] The semiconductor resist composition according to one embodiment can further contain a resin in addition to the organometallic compound, the chain carboxylic acid compound containing at least one carboxyl group, the cyclic carboxylic acid compound, and the solvent.

[0070] The resin may be a phenolic resin containing at least one aromatic moiety listed in Group 3 below. [ka]

[0071] The resin may have a weight average molecular weight of 500 to 20,000.

[0072] 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.

[0073] When the resin is contained in the above content range, excellent etching resistance and heat resistance can be obtained.

[0074] On the other hand, the semiconductor photoresist composition preferably comprises the organometallic compound, a chain carboxylic acid compound containing at least one carboxyl group, a cyclic carboxylic acid compound, a solvent, and a resin.

[0075] The semiconductor photoresist compositions according to the above-described embodiments may further include additives, such as surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0076] The surfactant may be, for example, but not limited to, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, or a combination thereof.

[0077] Examples of the crosslinking agent include, but are not limited to, melamine-based crosslinking agents, substituted iodine-based crosslinking agents, acrylic-based crosslinking agents, epoxy-based crosslinking agents, and polymer-based crosslinking agents. Examples of the crosslinking agent having at least two crosslink-forming substituents include methoxymethylated glycolyl, butoxymethylated glycolyl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, acrylic methacrylate, 1,4-butanediol diglycidyl ether, glycidol, diglycidyl 1,2-cyclohexanedicarboxylate, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated iodine, butoxymethylated iodine, and methoxymethylated thioiodine.

[0078] The leveling agent is used to improve the coating flatness during printing, and any known leveling agent that is commercially available can be used.

[0079] 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.

[0080] The quencher may be diphenyl(p-toluyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0081] The amount of these additives used can be easily adjusted depending on the desired physical properties, and they can also be omitted.

[0082] In addition, 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.

[0083] 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 wavelength of 5 nm to 40 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 to form a fine pattern having a width of, for example, 5 nm to 100 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] Subsequently, a composition for forming a resist underlayer film to form a resist underlayer film 104 is coated on the surface of the cleaned thin film 102 by spin coating. However, this is not intended to limit the scope of the present invention, 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.

[0089] The resist underlayer coating process can be omitted, and the case where the resist underlayer is coated will be described below.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] More specifically, the step of forming a pattern using the semiconductor photoresist composition may include a step of applying the above-described 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 step of drying the applied semiconductor photoresist composition to form a photoresist film 106.

[0094] The semiconductor photoresist composition has already been described in detail, so a duplicated description will be omitted.

[0095] 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.

[0096] Referring to FIG. 1(c), the photoresist film 106 is selectively exposed to light using a patterned mask 110.

[0097] For example, examples of light that can be used in the exposure process include light having wavelengths such as i-line (wavelength 365 nm), which is an activating radiation, KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), as well as light having high-energy wavelengths such as EUV (Extreme ultraviolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0098] More specifically, the exposure light according to one embodiment may be 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).

[0099] The exposed regions 106b of the photoresist film 106 form polymers through crosslinking reactions such as condensation between organometallic compounds, resulting in a different solubility from that of the unexposed regions 106a of the photoresist film 106.

[0100] 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.

[0101] 1(d) shows a photoresist pattern 108 formed by dissolving and removing the photoresist film 106a corresponding to the unexposed regions using a developer. Specifically, the photoresist film 106a corresponding to the unexposed regions is dissolved and removed using an organic solvent such as 2-heptanone, thereby completing the photoresist pattern 108 corresponding to the negative tone image.

[0102] 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.

[0103] 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.

[0104] As described above, the photoresist pattern 108 formed by exposure to high-energy light such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), EUV (Extreme ultraviolet; wavelength 13.5 nm), E-Beam (electron beam), etc. may have a thickness of 5 nm to 100 nm. For example, the photoresist pattern 108 may have a thickness of 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, or 5 nm to 20 nm.

[0105] Meanwhile, the photoresist pattern 108 may have a half-pitch of about 50 nm or less, e.g., 40 nm or less, e.g., 30 nm or less, e.g., 20 nm or less, e.g., 15 nm or less, and a pitch with a line width roughness of about 10 nm or less, about 5 nm or less, about 3 nm or less, or about 2 nm or less.

[0106] 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.

[0107] 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.

[0108] The thin film 102 may be etched by dry etching using an etching gas, such as CHF3, CF4, Cl2, BCl3, or a mixture thereof.

[0109] 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, the thin film pattern 114 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]

[0110] 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.

[0111] Synthesis of organometallic compounds Synthesis Example 1 340.7 g of t-butylSnPh and 300 g of propionic acid were placed in a 250 ml two-necked round-bottom flask and heated to reflux for 24 hours.

[0112] Unreacted propionic acid is removed under reduced pressure to obtain a compound represented by the following chemical formula 6. [ka]

[0113] Synthesis Example 2 10 g of dibutyltin dichloride was dissolved in 30 mL of ether, and then 70 mL of 1 M aqueous sodium hydroxide (NaOH) was added. The mixture was stirred for 1 hour. After stirring, the resulting solid was filtered, washed three times with 25 mL of deionized water, and then dried under reduced pressure at 100°C to obtain an organometallic compound with a weight-average molecular weight of 1,500, represented by the following chemical formula 7. [ka]

[0114] (Production of semiconductor photoresist composition) Examples 1 to 9, Comparative Examples 1 to 4 The organometallic compounds represented by Chemical Formula 6 and Chemical Formula 7 obtained in Synthesis Example 1 and Synthesis Example 2 were each dissolved in propylene glycol methyl ether acetate (PGMEA) at a concentration of 3%, and chain carboxylic acid compounds A1 and A2 and cyclic carboxylic acid compounds B1 to B3 were added and dissolved in the weight ratios shown in Table 1 below. The solution was then filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to produce semiconductor photoresist compositions according to Examples 1 to 9 and Comparative Examples 1 to 4.

[0115] [Table 1]

[0116] [ka] [ka]

[0117] Evaluation 1: Storage stability evaluation The storage stability of the organometallic compounds used in Examples 1 to 9 and Comparative Examples 1 to 4 was evaluated according to the following criteria, and the results are shown in Table 2 below.

[0118] [Storage stability] The semiconductor photoresist compositions according to Examples 1 to 9 and Comparative Examples 1 to 4 were left at room temperature (20±5°C) for a specific period of time, and the degree of precipitation was visually observed and evaluated according to the following storage standards.

[0119] *Evaluation criteria -◎: Can be stored for more than 4 months -○: Can be stored for 3 to 4 months -△: Can be stored for 2 weeks or more but less than 3 months -X: Can be stored for less than 2 weeks

[0120] Evaluation 2: Coating performance evaluation The photoresist compositions of Examples 1 to 9 and Comparative Examples 1 to 4 were spin-coated onto wafers at 1500 rpm for 60 seconds and baked at 110°C for 60 seconds to form thin films. The surface roughness of the thin films was measured from images taken with an atomic force microscope (AFM) or the like using software (e.g., optical profiler) according to the following criteria, and the results are shown in Table 2.

[0121] Among surface roughness parameters, root mean square roughness (Rq) refers to the root mean square (rms) of the vertical value within the reference length of the roughness profile.

[0122] [Evaluation criteria] -A:Rq 0.4nm or less -B: Rq exceeding 0.4nm 0.6nm or less -C:Rq exceeding 0.6nm

[0123] [Table 2]

[0124] From the results in Table 2, it can be seen that the patterns formed using the semiconductor photoresist compositions according to Examples 1 to 9 exhibit superior storage stability and coating properties compared to those of Comparative Examples 1 to 4.

[0125] 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 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]

[0126] 100...substrate, 102...thin film, 104...resist underlayer film, 106...photoresist film, 106a...unexposed area, 106b...exposed area, 108...photoresist pattern, 112...organic film pattern, 110...patterned mask, 114...thin film pattern.

Claims

1. Organometallic compounds; a chain carboxylic acid compound containing at least one carboxyl group; A cyclic carboxylic acid compound represented by the following chemical formula 1; and A composition for semiconductor photoresist, comprising a solvent: 【Chemistry 1】 In the above Chemical Formula 1, 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, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group; n1 is the number of substituents on A, from one to the maximum, Ring A is a substituted or unsubstituted C3 to C20 non-aromatic carbocyclic group or a substituted or unsubstituted C6 to C30 aromatic carbocyclic group; m1 is an integer of 1 to 3.

2. 2. The semiconductor photoresist composition of claim 1, wherein ring A is a substituted or unsubstituted cyclopentane group, a substituted or unsubstituted cyclohexane group, a substituted or unsubstituted heptane group, a substituted or unsubstituted octane group, a substituted or unsubstituted cyclopentene group, a substituted or unsubstituted cyclohexene group, a substituted or unsubstituted benzene group, a substituted or unsubstituted naphthalene group, a substituted or unsubstituted anthracene group, a substituted or unsubstituted phenanthrene group, a substituted or unsubstituted pyrene group, a substituted or unsubstituted triphenylene group, or a combination thereof.

3. 2. The semiconductor photoresist composition according to claim 1, wherein the cyclic carboxylic acid compound is represented by the following Chemical Formula 1A or Chemical Formula 1B: 【Chemistry 2】 In Chemical Formula 1A or Chemical Formula 1B, R ４ ~R １９ are each independently a hydrogen atom, 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, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group; R ４ ~R １４ at least one of 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, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group; R １５ ~R １９ At least one of the 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, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group.

4. The R ４ ~R １４ at least one of is a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted pentyl group, or a combination thereof; The R １５ ~R １９ wherein at least one of the groups selected from the group consisting of a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted pentyl group, or a combination thereof.

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

6. 2. The semiconductor photoresist composition according to claim 1, wherein the chain carboxylic acid compound is represented by the following chemical formula 2: 【Chemistry 4】 In the above Chemical Formula 2, R ２ and R ３ are each independently a hydrogen atom, a hydroxy group, a carboxyl group, 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, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group; L １ and L ２ each independently represents a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C3 to C20 cycloalkenylene group, or a substituted or unsubstituted C6 to C20 arylene group; n2 and n3 each independently represent an integer from 0 to 5; m2 and m3 each independently represent an integer of 0 or 1; m2+m3 are integers equal to or greater than 1, When n2 and n3 are each an integer of 2 or more, each L １ and L ２ are the same or different from each other.

7. The R ２ and R ３ 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 isopropyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted pentyl group, or a combination thereof.

8. Said L １ and L ２ are each independently a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, a substituted or unsubstituted pentylene group, a substituted or unsubstituted cyclopentylene group, a substituted or unsubstituted cyclopentenylene group, a substituted or unsubstituted cyclopentadienylene group, or a substituted or unsubstituted cyclohexylene group.

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

10. 2. The semiconductor photoresist composition according to claim 1, wherein the chain carboxylic acid compound and the cyclic carboxylic acid compound are contained in a weight ratio of 9:1 to 1:

9.

11. 2. The semiconductor photoresist composition according to claim 1, wherein the chain carboxylic acid compound and the cyclic carboxylic acid compound are contained in an amount of 0.01 to 20% by weight, based on 100% by weight of the semiconductor photoresist composition.

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

13. 10. The semiconductor photoresist composition of claim 1, further comprising an additive selected from the group consisting of a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, and combinations thereof.

14. 2. The semiconductor photoresist composition according to claim 1, wherein the organometallic compound is an organotin compound containing at least one of an organic oxy group and an organic carbonyl oxy group.

15. 2. The composition for semiconductor photoresist of claim 1, wherein the organometallic compound is represented by the following chemical formula 3: 【Transformation 6】 In the above Chemical Formula 3, R ２０ is selected from among a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, and a substituted or unsubstituted C7 to C30 arylalkyl group; R ２１ ~R ２３ are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, alkoxy, and aryloxy (-OR 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, or a combination thereof), a carboxyl group (—O(C═O)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, 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, 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, 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, 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, or a combination thereof) or a thiocarboxyl group (—SCO)R ｌ , R ｌ is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R ２１ ~R ２３ At least one of the groups is 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, or a combination thereof), a carboxyl group (—O(C═O)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, 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, 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, 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, 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, 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, or a combination thereof.

16. The R ２１ ~R ２３ At least one of the groups is alkoxy and aryloxy (—OR ｂ , where R ａ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), and a carboxyl group (—O(C═O)R ｃ , R ｃ is selected from hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.

17. The R ２０ is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group containing one or more double or triple bonds, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C4 to C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof; R ｂ is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof; R ｃ is hydrogen, a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.

18. 2. The composition for semiconductor photoresist of claim 1, wherein the organometallic compound is represented by the following Chemical Formula 4 or Chemical Formula 5: 【Transformation 7】 In the above Chemical Formula 4, R ２４ is a C1 to C31 hydrocarbyl group, where 0<z≦2 and 0<(z+x)≦4; 【Transformation 8】 In the above Chemical Formula 5, R ２５ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 aliphatic unsaturated organic group containing one or more double or triple bonds, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof; X is sulfur (S), selenium (Se), or tellurium (Te); Y is -OR ｍ or -O(C=O)R ｎ and The R ｍ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R ｎ is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; The a, b, c, and d are each independently an integer of 1 to 20.

19. forming a film to be etched on a substrate; Applying the semiconductor photoresist composition according to any one of claims 1 to 18 onto the film to be etched to form a photoresist film; patterning the photoresist film to form a photoresist pattern; and A pattern forming method comprising: etching the target layer using the photoresist pattern as an etching mask.

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