Composition for semiconductor photoresist and patterning method using the same

Abstract

To provide a composition for semiconductor photoresist with superior sensitivity properties.SOLUTION: A composition for semiconductor photoresist contains an organic metal compound, a vinyl group-containing acid compound and a solvent.SELECTED DRAWING: Figure 5

Description

[Technical field]

[0001] This disclosure relates to a semiconductor photoresist composition and a patterning 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 performing spatial resolutions below 16 nm. Currently, traditional chemically amplified (CA) photoresists struggle to meet the specifications for resolution, photospeed, and 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 fact that has long been known in 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 absorbance of the photoresist at 13.5 nm wavelengths, thereby reducing sensitivity.

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

[0006] In order to overcome the disadvantages of the above-mentioned chemically amplified organic photosensitive compositions, inorganic photosensitive compositions have been researched. Inorganic photosensitive compositions are mainly used for negative tone patterning, which is resistant to removal by developer compositions due to chemical modification by non-chemically amplified mechanisms. Inorganic compositions contain inorganic elements with higher EUV absorption rate than hydrocarbons, so they can ensure sensitivity even in non-chemically amplified mechanisms, and are known to have less line edge roughness and fewer defects because they are less sensitive to stochastic effects.

[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 (US5061599,; H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298-300, 1986).

[0008] These materials have been effective in patterning large features in a bilayer configuration with deep UV, x-ray, and electron beam sources. More recently, impressive performance has been shown when using cationic hafnium metal oxide sulfate (HfSOx) materials with peroxo complexing agents to image 15 nm half pitch (HP) with projection EUV exposure (US2011-0045406,; JK Stowers, A. Telecky, M. Kocsis, BL Clark, DA Keszler, A. Grenville, CN Anderson, PP Naulleau, Proc. SPIE, 7969, 796915, 2011). This system shows the best performance of a non-CA photoresist and has a photospeed approaching the requirements for a viable EUV photoresist. However, hafnium metal oxide sulfate materials with peroxo complexing agents have some practical drawbacks. First, the materials are coated with a highly corrosive sulfuric acid / hydrogen peroxide mixture, which results in poor shelf-life stability. Second, it is a complex mixture and cannot be easily modified to improve performance. Third, it must be developed with a very high concentration of, for example, 25 wt% TMAH (tetramethylammonium hydroxide) solution.

[0009] Recently, active research has been conducted on molecules containing tin, which are known to have excellent absorption of extreme ultraviolet rays. In the case of organotin polymers, which are one of them, alkyl ligands are dissociated by light absorption or secondary electrons generated by the absorption, and crosslinking with surrounding chains through oxo bonds allows negative tone patterning that is not removed by organic developers. Such organotin polymers have shown a dramatic improvement in sensitivity while maintaining resolution and line edge roughness, but further improvement in the patterning properties is required for commercialization. Summary of the Invention [Problem to be solved by the invention]

[0010] An object of one embodiment is to provide a composition for semiconductor photoresist having excellent sensitivity characteristics.An object of another embodiment is to provide a method for forming a pattern using the composition for semiconductor photoresist. [Means for solving the problem]

[0011] A composition for a semiconductor photoresist according to one embodiment includes an organometallic compound; a vinyl group-containing acid compound, and a solvent.

[0012] The vinyl-containing acid compound may contain one or more of at least one carboxyl group, at least one sulfonic acid group, and at least one phosphonic acid group.

[0013] The vinyl group-containing acid compound may be represented by any one of the following formulas 1 to 3.

[0014] [ka]

[0015] In the above Chemical Formula 1 to Chemical Formula 3, R 1 ~R 3are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group, L 1 ~L 3 are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a substituted or unsubstituted C6 to C20 arylene group, n1 to n3 each independently represents an integer of 1 or more.

[0016] R 1 ~R 3 are each independently hydrogen or a substituted or unsubstituted C1 to C5 alkyl group, L 1 ~L 3 may each independently be a single bond, a substituted or unsubstituted C1-C5 alkylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group.

[0017] The vinyl group-containing acid compound may be one or more selected from 4-vinylbenzoic acid, vinylsulfonic acid, vinylphosphonic acid, vinylacetic acid, (meth)acrylic acid, and 1-vinylpyrazole-4-carboxylic acid.

[0018] The vinyl group-containing acid compound may be contained in an amount of 0.1 to 15% by weight based on 100% by weight of the semiconductor photoresist composition.

[0019] The organometallic compound may be included in an amount of 1 to 30% by weight based on 100% by weight of the composition for semiconductor photoresist.

[0020] The organometallic compound may include tin (Sn).

[0021] The organometallic compound may include at least one of an organic oxy group and an organic carbonyloxy group.

[0022] The organometallic compound may be represented by the following Chemical Formula 4.

[0023] [ka]

[0024] In the above Chemical Formula 4, R 4 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, and L a -OR a (Here, L a is a substituted or unsubstituted C1 to C20 alkylene group, R a is a substituted or unsubstituted C1 to C20 alkyl group; R 5 ~R 7 are each independently -OR b or -OC(=O)R c is selected from among 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; 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.

[0025] R 4is a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C4-C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof; R a is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof; R b may be hydrogen, a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.

[0026] R 4 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 ethynyl group, a propynyl group, a butynyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pentanoyl group, an ethoxy group, a propoxy group, or a combination thereof; R a is an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propenyl group, a butenyl group, an ethynyl group, a propynyl group, a butynyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, or a combination thereof; R bcan be hydrogen, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylene, benzyl, or combinations thereof.

[0027] The organometallic compound and the vinyl group-containing acid compound may be contained in a weight ratio of 99:1 to 80:20.

[0028] The semiconductor photoresist composition may further include additives such as a surfactant, a leveling agent, a crosslinking agent, or a combination thereof.

[0029] According to another embodiment, a method for forming a pattern includes forming a film to be etched on a substrate, applying the above-described semiconductor photoresist composition on the film to be etched to form a photoresist film, patterning the photoresist film to form a photoresist pattern, and etching the film to be etched using the photoresist pattern as an etching mask.

[0030] The step of forming the photoresist pattern may use light having a wavelength of 5 nm to 150 nm.

[0031] The method of forming a pattern may further include providing a resist underlayer film formed between the substrate and the photoresist film.

[0032] The photoresist pattern may have a width of 5 nm to 100 nm. Effect of the Invention

[0033] The semiconductor photoresist composition according to one embodiment can achieve excellent sensitivity. [Brief description of the drawings]

[0034] [Figure 1] 1 is a cross-sectional view illustrating a method for forming a pattern using a semiconductor photoresist composition according to an embodiment. [Diagram 2] 1 is a cross-sectional view illustrating a method for forming a pattern using a semiconductor photoresist composition according to an embodiment. [Diagram 3] 1 is a cross-sectional view illustrating a method for forming a pattern using a semiconductor photoresist composition according to an embodiment. [Figure 4] 1 is a cross-sectional view illustrating a method for forming a pattern using a semiconductor photoresist composition according to an embodiment. [Diagram 5] 1 is a cross-sectional view illustrating a method for forming a pattern using a semiconductor photoresist composition according to an embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0035] Hereinafter, the embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, in the description, the description of the functions or configurations that are already known will be omitted in order to clarify the gist of the description.

[0036] In order to clearly explain the present description, parts unnecessary for the description are omitted, and the same or similar components are designated by the same reference numerals throughout the specification. Furthermore, the size and thickness of each component shown in the drawings are arbitrarily shown for the convenience of explanation, and the present description is not necessarily limited to those shown in the drawings.

[0037] In the drawings, the thickness of a plurality of layers and regions is exaggerated to clearly show the layers and regions. For convenience of explanation in the drawings, the thickness of some layers and regions is exaggerated. When a layer, film, region, plate, or other part is said to be "on" another part, this includes not only the case where it is "directly on" the other part, but also the case where there is another part therebetween.

[0038] In this description, "substituted" means that a hydrogen atom is replaced by a deuterium atom, a halogen group, a hydroxy 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 C6 to C30 aromatic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group). "Unsubstituted" means that the hydrogen atom is not substituted with another substituent and remains as a hydrogen atom.

[0039] As used herein, unless otherwise specified, the term "alkyl group" refers to a straight or branched chain aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0040] 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.

[0041] In this description, unless otherwise defined, a "cycloalkyl group" refers to a monovalent cyclic aliphatic saturated hydrocarbon group.

[0042] The cycloalkyl group can be a C3-C8 cycloalkyl group, such as a C3-C7 cycloalkyl group, a C3-C6 cycloalkyl group, a C3-C5 cycloalkyl group, or a C3-C4 cycloalkyl group. For example, the cycloalkyl group can be, but is not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

[0043] As used herein, "aliphatically unsaturated organic group" refers to a hydrocarbon group in which the bonds between carbon atoms in the molecule are double bonds, triple bonds, or a combination thereof.

[0044] The aliphatic unsaturated organic group may be a C2-C8 aliphatic unsaturated organic group. For example, the aliphatic unsaturated organic group may be a C2-C7 aliphatic unsaturated organic group, a C2-C6 aliphatic unsaturated organic group, a C2-C5 aliphatic unsaturated organic group, or a C2-C4 aliphatic unsaturated organic group. For example, the C2-C4 aliphatic unsaturated organic group may be a vinyl group, an ethynyl group, an allyl group, a 1-propenyl group, a 1-methyl-1-propenyl group, a 2-propenyl group, a 2-methyl-2-propenyl group, a 1-propynyl group, a 1-methyl-1propynyl group, a 2-propynyl group, a 2-methyl-2-propynyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group.

[0045] As used herein, an "aryl group" refers to a substituent in which all elements of the cyclic substituent have p-orbitals that form conjugation, and includes monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of carbon atoms) functional groups.

[0046] 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 through a sigma bond, or, if the heteroaryl group contains two or more rings, the two or more rings may be fused together. If the heteroaryl group is a fused ring, each ring may contain 1 to 3 of the heteroatoms.

[0047] As used herein, unless otherwise defined, an "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.

[0048] As used herein, unless otherwise defined, an "alkynyl group" refers to an aliphatic unsaturated alkynyl group which is a straight-chain or branched-chain aliphatic hydrocarbon group and contains one or more triple bonds.

[0049] Hereinafter, a composition for semiconductor photoresist according to an embodiment will be described.

[0050] A composition for semiconductor photoresist according to an embodiment of the present invention may include an organometallic compound, a vinyl group-containing acid compound, and a solvent.

[0051] The semiconductor photoresist composition may include a vinyl group-containing acid compound, so that a polymerization reaction is carried out by radicals generated by EUV light, thereby improving sensitivity characteristics.

[0052] The vinyl-containing acid compound may contain one or more of at least one carboxyl group, at least one sulfonic acid group, and at least one phosphonic acid group.

[0053] The vinyl group-containing acid compound may be represented by any one of the following formulas 1 to 3.

[0054] [ka]

[0055] In the above Chemical Formula 1 to Chemical Formula 3, R 1 ~R 3 are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group, L 1 ~L 3 are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a substituted or unsubstituted C6 to C20 arylene group, n1 to n3 each independently represents an integer of 1 or more.

[0056] In one embodiment, the L 1 ~L 3 are each a single bond, the carboxyl group, the sulfonic acid group and the phosphonic acid group may each be substituted with one group, and in this case, n1 to n3 each may be 1.

[0057] In one embodiment, the L 1 ~L 3 are each independently a substituted or unsubstituted C1 to C10 alkylene group, the carboxyl group, sulfonic acid group and phosphonic acid group may each be mono- or di-substituted, and in this case, n1 to n3 may each independently be an integer of 1 or 2.

[0058] In one embodiment, the L 1 ~L 3are each independently a substituted or unsubstituted C6 to C20 arylene group, the carboxyl group, sulfonic acid group and phosphonic acid group may each be substituted with a sheet that can be substituted with the C6 to C20 arylene group, and for example, n1 to n3 may each independently be one of integers from 1 to 10. Specifically, n1 to n3 may each independently be one of integers from 1 to 8. More specifically, n1 to n3 may each independently be one of integers from 1 to 5. For example, n1 to n3 may each independently be one of integers from 1 to 3.

[0059] R 1 ~R 3 are each independently hydrogen or a substituted or unsubstituted C1 to C5 alkyl group, L 1 ~L 3 may each independently be a single bond, a substituted or unsubstituted C1-C5 alkylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group.

[0060] The vinyl group-containing acid compound may be one or more selected from 4-vinylbenzoic acid, vinylsulfonic acid, vinylphosphonic acid, vinylacetic acid, (meth)acrylic acid, and 1-vinylpyrazole-4-carboxylic acid.

[0061] The vinyl group-containing acid compound may be contained in an amount of 0.1 to 15% by weight based on 100% by weight of the semiconductor photoresist composition.

[0062] The organometallic compound may be included in an amount of 1 to 30% by weight based on 100% by weight of the composition for semiconductor photoresist.

[0063] The organometallic compound may include tin (Sn).

[0064] The organometallic compound may include at least one of an organic oxy group and an organic carbonyloxy group.

[0065] The organometallic compound may be represented by the following Chemical Formula 4.

[0066] [ka]

[0067] In the above Chemical Formula 4, R 4 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, and L a -OR a (Here, L a is a substituted or unsubstituted C1 to C20 alkylene group, R a is a substituted or unsubstituted C1 to C20 alkyl group; R 5 ~R 7 are each independently -OR b or -OC(=O)R c is selected from among 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; 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.

[0068] Meanwhile, the compound represented by the formula 4 has a ligand -OR bor -OC(=O)R c By including the compound, a pattern formed using a semiconductor photoresist composition containing the compound can exhibit excellent limit resolution.

[0069] Also, -OR b or -OC(=O)R c The ligand can determine the solubility of the compound represented by Chemical Formula 4 in a solvent.

[0070] R 4 is a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C4-C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof; R a is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof; R b may be hydrogen, a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.

[0071] R 4is a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propenyl group, a butenyl group, an ethynyl group, a propynyl group, a butynyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pentanoyl group, an ethoxy group, a propoxy group, or a combination thereof; R a is an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propenyl group, a butenyl group, an ethynyl group, a propynyl group, a butynyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, or a combination thereof; R b can be hydrogen, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylene, benzyl, or combinations thereof.

[0072] The semiconductor photoresist composition according to one embodiment may contain the organometallic compound and the vinyl group-containing acid compound in a weight ratio of 99:1 to 80:20. For example, the semiconductor photoresist composition may contain the organometallic compound and the vinyl group-containing acid compound in a weight ratio of 95:5 to 85:15.

[0073] When the weight ratio of the organometallic compound to the vinyl group-containing acid compound satisfies the above range, a semiconductor photoresist composition having excellent sensitivity can be provided.

[0074] The composition for semiconductor photoresist according to one embodiment includes the organometallic compound and the vinyl group-containing acid compound in the above content ranges, thereby improving the sensitivity of the photoresist.

[0075] The solvent included in the semiconductor photoresist composition according to an embodiment may be an organic solvent, and examples thereof 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.

[0076] The composition for a semiconductor resist according to an embodiment may further include a resin in addition to the organometallic compound, the vinyl group-containing acid compound, and the solvent.

[0077] The resin may be a phenolic resin containing at least one aromatic moiety listed in Group 2 below.

[0078] [ka]

[0079] The resin may have a weight average molecular weight of 500 to 20,000.

[0080] The resin may be included in an amount of 0.1% by weight to 50% by weight based on the total content of the composition for semiconductor photoresist.

[0081] When the resin is contained within the above content range, excellent etching resistance and heat resistance can be obtained.

[0082] Meanwhile, the semiconductor photoresist composition preferably comprises the organometallic compound, a solvent, and a resin as described above. However, the semiconductor photoresist composition according to the above-described embodiment may further include an additive, if necessary. Examples of the additive include a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, or a combination thereof.

[0083] The surfactant may be, for example, but is not limited to, an alkylbenzenesulfonate, an alkylpyridinium salt, a polyethylene glycol, a quaternary ammonium salt, or a combination thereof.

[0084] Examples of the crosslinking agent include, but are not limited to, melamine-based crosslinking agents, substituted urea-based crosslinking agents, acrylic-based crosslinking agents, epoxy-based crosslinking agents, or polymer-based crosslinking agents. Examples of the crosslinking agent having at least two crosslinking-forming substituents 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, or methoxymethylated thiourea.

[0085] The leveling agent is used to improve coating flatness during printing, and any known leveling agent that is commercially available can be used.

[0086] 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 fluorides, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or combinations thereof.

[0087] The quencher may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or combinations thereof.

[0088] The amount of these additives used can be easily adjusted depending on the desired physical properties, or they can be omitted.

[0089] In addition, the semiconductor photoresist composition may further use a silane coupling agent as an additive to enhance adhesion to a substrate (for example, to enhance adhesion of the semiconductor photoresist composition to a substrate). The silane coupling agent may be, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; or a carbon-carbon unsaturated bond-containing silane compound such as trimethoxy[3-(phenylamino)propyl]silane, but is not limited thereto.

[0090] The semiconductor photoresist composition can form a pattern having a high aspect ratio without causing pattern collapse. Therefore, in order to form a fine pattern having a width of, for example, 5 nm to 100 nm, for example, a fine pattern having a width of, for example, 5 nm to 80 nm, for example, a fine pattern having a width of, for example, 5 nm to 70 nm, for example, a fine pattern having a width of, for example, 5 nm to 50 nm, for example, a fine pattern having a width of, for example, 5 nm to 40 nm, for example, a fine pattern having a width of, for example, 5 nm to 30 nm, for example, a fine pattern having a width of, for example, 5 nm to 20 nm, the composition can be used in a photoresist process using light having a wavelength of, for example, 5 nm to 150 nm, for example, a photoresist process using light having a wavelength of, for example, 5 nm to 100 nm, for example, a photoresist process using light having a wavelength of, for example, 5 nm to 80 nm, for example, a photoresist process using light having a wavelength of, for example, 5 nm to 50 nm, for example, a photoresist process using light having a wavelength of, for example, 5 nm to 30 nm, for example, a photoresist process using light having a wavelength of, for example, 5 nm to 20 nm. Therefore, by using the semiconductor photoresist composition according to one embodiment, extreme extreme UV lithography using an EUV light source with a wavelength of about 13.5 nm can be realized.

[0091] Meanwhile, according to another embodiment, there may be provided a method for forming a pattern using the above-described semiconductor photoresist composition. For example, the formed pattern may be a photoresist pattern.

[0092] According to an embodiment, a method for forming a pattern includes forming a film to be etched on a substrate, applying the above-described semiconductor photoresist composition on the film to be etched to form a photoresist film, patterning the photoresist film to form a photoresist pattern, and etching the film to be etched using the photoresist pattern as an etching mask.

[0093] Hereinafter, a method for forming a pattern using the above-mentioned semiconductor photoresist composition will be described with reference to Figures 1 to 5. Figures 1 to 5 are cross-sectional views illustrating a method for forming a pattern using the semiconductor photoresist composition according to the present invention.

[0094] Referring to FIG. 1, an object to be etched is first prepared. An example of the object to be etched may be a thin film 102 formed on a semiconductor substrate 100. Hereinafter, only the case where the object to be etched 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.

[0095] Next, a composition for forming a resist underlayer film is coated by applying a spin coating method on the surface of the cleaned thin film 102 to form a resist underlayer film 104. However, an embodiment is not necessarily 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.

[0096] Although the resist underlayer coating process can be omitted, the following description will be made on the case where the resist underlayer is coated.

[0097] Thereafter, drying and baking steps are performed to form a resist underlayer film 104 on the thin film 102. The baking process can be performed at about 100 to about 500°C, for example, about 100 to about 300°C.

[0098] The resist underlayer film 104 is formed between the substrate 100 and the photoresist film 106 to prevent the 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.

[0099] 2, 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.

[0100] More specifically, the step of forming a pattern using the semiconductor photoresist composition may include a step of applying the above-mentioned semiconductor photoresist composition onto the substrate 100 on which the thin film 102 is 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.

[0101] The semiconductor photoresist composition has already been described in detail, so a duplicated description will be omitted.

[0102] 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.

[0103] Referring to FIG. 3, the photoresist film 106 is selectively exposed to light using a patterned mask 110 .

[0104] As an example, examples of light that can be used in the exposure process include light having short wavelengths such as activation radiation i-line (wavelength 365 nm), 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).

[0105] More specifically, the exposure light according to an embodiment may be short-wavelength light having a wavelength range of 5 nm to 150 nm, and may be light having a high-energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0106] The exposed regions 106a of the photoresist film 106 form polymers through a crosslinking reaction, such as condensation between organometallic compounds, and thus have different solubilities from the unexposed regions 106b of the photoresist film 106.

[0107] 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 106a of the photoresist film 106 becomes difficult to dissolve in a developer.

[0108] 4 shows a photoresist pattern 108 formed by dissolving and removing the photoresist film 106b corresponding to the unexposed region using a developer. Specifically, the photoresist film 106b corresponding to the unexposed region is dissolved and removed using an organic solvent such as 2-heptanone, completing the photoresist pattern 108 corresponding to the negative tone image.

[0109] 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.

[0110] However, the photoresist pattern according to an embodiment is not necessarily limited to being formed as a negative tone image, but may be formed to have 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.

[0111] 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), ArF excimer laser (wavelength 193 nm), as well as high-energy light such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam) may have a thickness width of 5 nm to 100 nm. As an example, the photoresist pattern 108 may be formed with a thickness 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.

[0112] 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 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.

[0113] Next, the resist underlayer film 104 is etched using the photoresist pattern as an etching mask. Through this etching process, an organic layer pattern 112 is formed. The formed organic layer pattern 112 may also have a width corresponding to the photoresist pattern .

[0114] 5, 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.

[0115] The thin film 102 can be etched by dry etching using an etching gas such as CHF3, CF4, Cl2, BCl3, or a mixture thereof.

[0116] The thin film pattern 114 formed by using the photoresist pattern 108 formed by the exposure process performed using an EUV light source in the previous exposure process may have a width corresponding to the photoresist pattern 108. As an 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 performed 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 be formed with a width of 20 nm or less. EXAMPLES

[0117] The present invention will be described in more detail with reference to the following examples of preparing the above-mentioned semiconductor photoresist composition, but the technical features of the present invention are not limited to the following examples.

[0118] Synthesis of organometallic compounds Synthesis Example 1 Dissolve 20g (51.9mmol) of Ph3SnCl in 70ml of THF (tetrahydrofuran) in a 250ml two-necked round-bottom flask and lower the temperature to 0°C in an ice bath. Then, slowly add 1M THF solution (62.3mmol) of butylmagnesium chloride (BuMgCl). After the addition is complete, stir at 25°C for 12 hours to obtain the compound represented by the following chemical formula 5a.

[0119] [ka]

[0120] Then, 10 g (24.6 mmol) of the compound of formula 5a is dissolved in 50 mL of CH2Cl2, and 3 equivalents (73.7 mmol) of 2M HCl diethyl ether solution is slowly added dropwise for 30 minutes at -78°C. After stirring for 12 hours at 25°C, the solvent is concentrated and vacuum distilled to obtain the compound represented by the following formula 5b.

[0121] [ka]

[0122] Then, 25 mL of acetic acid is slowly added dropwise to 10 g (25.6 mmol) of the compound of formula 5b at 25° C., and the mixture is heated to reflux for 12 hours. After increasing the temperature to 25° C., the acetic acid is vacuum distilled to finally obtain the compound represented by formula 5 below.

[0123] [ka]

[0124] Synthesis Example 2 10 g (24.6 mmol) of the compound of formula 5a is dissolved in 50 mL of CH2Cl2, and 3 equivalents (73.7 mmol) of 2M HCl diethyl ether solution is slowly added dropwise for 30 minutes at -78°C. After stirring for 12 hours at 25°C, the solvent is concentrated and vacuum distilled to obtain the compound represented by the following formula 6b.

[0125] [ka]

[0126] Then, 10 g (25.6 mmol) of the compound of formula 6b is mixed with 25 mL of a mixture of propionic acid and methacrylic acid (volume ratio = 3:1) and heated under reflux for 12 hours. After increasing the temperature to 25°C, the mixture is vacuum distilled to finally obtain the compound represented by formula 6 below.

[0127] [ka]

[0128] Synthesis Example 3 Put 3.7g of Mg into a 500mL round-bottom flask, dry it under vacuum, add I2 and add 120mL of THF. Dilute 8.76g of 1,4-bis(bromomethyl)benzene and 20g of tributyltin chloride in 120mL of THF and gradually add it to the previous round-bottom flask and stir. Then wash with NH4Cl solution and NaCl solution, dry it, dissolve it in toluene, add 4.3g (16.7mmol) of SnCl4 slowly at low temperature and stir for 2 hours. After removing the solvent, extraction is performed using acetonitrile and pentene, the acetonitrile layer is collected, the solvent is removed, and then it is added to DCM again and slowly added with stirring 1.625g of triethylamine, then acetic acid is added at low temperature and stirred for 1 hour. After that, the solid is removed by a filter, and the compound represented by formula 7 is obtained through concentration.

[0129] [ka]

[0130] (Production of semiconductor photoresist composition) Examples 1 to 7 and Comparative Examples 1 to 5 The compounds represented by Chemical Formulae 5 to 7 obtained in Synthesis Examples 1 to 3 and the acid compound were dissolved in propylene glycol methyl ether acetate at a concentration of 3 wt % in the weight ratios shown in Table 1 below, and filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to produce semiconductor photoresist compositions according to Examples 1 to 7 and Comparative Examples 1 to 5.

[0131] A circular silicon wafer with a diameter of 4 inches having a native oxide surface is used as a substrate for thin film coating, and is treated with a UV ozone cleaning system for 10 minutes before coating the thin film. The semiconductor photoresist compositions according to Examples 1 to 7 and Comparative Examples 1 to 5 are spin-coated on the treated substrate at 1500 rpm for 30 seconds, and baked at 110° C. for 60 seconds (post-apply bake, PAB) to form a photoresist thin film.

[0132] The thickness of the film after coating and baking was measured via ellipsometry and was measured to be about 25 nm.

[0133] 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 7 and Comparative Examples 1 and 5. Pad exposure times were adjusted so that an incremental EUV dose was applied to each pad.

[0134] The resist and substrate were then post-exposure baked (PEB) on a hotplate at 160°C for 120 seconds. The baked films were 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 areas. The process was terminated by a final hotplate bake at 150°C for 2 minutes.

[0135] 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 completed) was evaluated for each type of resist according to the following criteria and shown in Table 1. *Evaluation criteria (Dg value) A: 16 mJ / cm 2 less than B: 16 mJ / cm 2 End

[0136] [Table 1]

[0137] It can be seen from the results in Table 1 that the patterns formed using the semiconductor photoresist compositions according to Examples 1 to 7 exhibit superior sensitivity compared to Comparative Examples 1 to 5.

[0138] Although specific embodiments of the present invention have been described and illustrated above, it is obvious 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 or variations should not be understood individually from the technical spirit and perspective of the present invention, and the modified embodiments should be considered to belong to the scope of the claims of the present invention. [Explanation of symbols]

[0139] 100...substrate, 102...thin film, 104...resist underlayer film, 106...photoresist film, 106a...exposed area, 106b...unexposed area, 108...photoresist pattern, 112...organic film pattern, 110...patterned mask, 114...thin film pattern.

Claims

1. Organometallic compounds; Vinyl-containing acid compounds and A composition for semiconductor photoresist comprising a solvent.

2. 2. The semiconductor photoresist composition according to claim 1, wherein the vinyl group-containing acid compound contains one or more of at least one carboxyl group, at least one sulfonic acid group, and at least one phosphonic acid group.

3. 2. The composition for semiconductor photoresist according to claim 1, wherein the vinyl group-containing acid compound is represented by any one of the following formulas 1 to 3: 【Chemistry 1】 (In the above Chemical Formula 1 to Chemical Formula 3, R １ ~R ３ are each independently hydrogen or a substituted or unsubstituted C1-C10 alkyl group; L １ ~L ３ are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a substituted or unsubstituted C6 to C20 arylene group; n1 to n3 are each independently an integer of 1 or more.

4. The R １ ~R ３ are each independently hydrogen or a substituted or unsubstituted C1-C5 alkyl group; Said L １ ~L ３ each independently represents a single bond, a substituted or unsubstituted C1 to C5 alkylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group.

5. 2. The composition for semiconductor photoresist according to claim 1, wherein the vinyl group-containing acid compound is at least one selected from the group consisting of 4-vinylbenzoic acid, vinylsulfonic acid, vinylphosphonic acid, vinylacetic acid, (meth)acrylic acid, and 1-vinylpyrazole-4-carboxylic acid.

6. 2. The semiconductor photoresist composition according to claim 1, wherein the vinyl group-containing acid compound is contained in an amount of 0.1 to 15% by weight based on 100% by weight of the semiconductor photoresist composition.

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

8. 2. The semiconductor photoresist composition according to claim 1, wherein the organometallic compound contains tin (Sn).

9. 2. The semiconductor photoresist composition according to claim 1, wherein the organometallic compound contains at least one of an organic oxy group and an organic carbonyloxy group.

10. The composition for semiconductor photoresist according to claim 1 , wherein the organometallic compound is represented by the following formula 4: 【Chemistry 2】 (In the above Chemical Formula 4, R ４ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, and L ａ -O-R ａ (Here, L ａ is a substituted or unsubstituted C1 to C20 alkylene group, R ａ is a substituted or unsubstituted C1-C20 alkyl group; R ５ ~R ７ Each independently represents -OR ｂ Or -OC(=O)R ｃ is selected from among 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; 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.

11. The R ４ is a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 aliphatic unsaturated organic group containing one or more double or triple bonds, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C4-C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof; The R ａ is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof; The R ｂ is hydrogen, a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.

12. The R ４ 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 ethynyl group, a propynyl group, a butynyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pentanoyl group, an ethoxy group, a propoxy group, or a combination thereof; The R ａ is an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propenyl group, a butenyl group, an ethynyl group, a propynyl group, a butynyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, or a combination thereof; The R ｂ is hydrogen, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propenyl group, a butenyl group, an ethynyl group, a propynyl group, a butynyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, or a combination thereof.

13. 2. The semiconductor photoresist composition according to claim 1, comprising said organometallic compound and said vinyl group-containing acid compound in a weight ratio of 99:1 to 80:

20.

14. 10. The semiconductor photoresist composition of claim 1, further comprising an additive of a surfactant, a crosslinker, a leveling agent, an organic acid, a quencher, or a combination thereof.

15. forming a film to be etched on a substrate; Applying the composition for semiconductor photoresist according to any one of claims 1 to 14 onto the film to be etched to form a photoresist film; patterning the photoresist film to form a photoresist pattern; and The method of forming a pattern includes etching the layer to be etched using the photoresist pattern as an etching mask.

16. 16. The method of claim 15, wherein the forming of the photoresist pattern uses light having a wavelength of 5 nm to 150 nm.

17. The method of claim 15, further comprising providing a resist underlayer film formed between the substrate and the photoresist film.

18. The pattern forming method according to claim 15, wherein the photoresist pattern has a width of 5 nm to 100 nm.

Images