Composition for semiconductor photoresist, and pattern formation method using same

Abstract

The present invention relates to: a composition for a semiconductor photoresist, the composition comprising an organometallic compound, a solvent, and a cyclic organic acid having an electron withdrawing group (EWG); and a pattern formation method using the composition.

Description

Composition for semiconductor photoresist and method for forming a pattern using the same

[0001] The present invention relates to a composition for semiconductor photoresist and a method for forming a pattern using the same.

[0002] Extreme ultraviolet (EUV) lithography is attracting attention as a key technology for manufacturing next-generation semiconductor devices. EUV lithography is a pattern-forming technology that utilizes EUV light with a wavelength of 13.5 nm as an exposure light source. EUV lithography has been demonstrated to be capable of forming extremely fine patterns (e.g., 20 nm or less) during the exposure process of semiconductor device manufacturing.

[0003] The implementation of extreme ultraviolet (EUV) lithography requires the development of compatible photoresists capable of performing at spatial resolutions down to 16 nm. Currently, conventional chemically amplified (CA) photoresists struggle to meet the resolution, photospeed, feature roughness, and line edge roughness (LER) specifications for next-generation devices.

[0004] Intrinsic image blur due to acid-catalyzed reactions in these polymeric photoresists limits resolution at small feature sizes, a problem long known in electron-beam lithography. Chemically amplified (CA) photoresists are designed for high sensitivity, but can struggle more under EUV exposure, in part because their typical elemental makeup lowers their absorbance at a wavelength of 13.5 nm, thereby reducing their sensitivity.

[0005] CA photoresists can also suffer from roughness issues at small feature sizes, and experimentally have shown that line edge roughness (LER) increases with decreasing photospeed, partly due to the nature of acid-catalyzed processes. Due to the shortcomings and issues with CA photoresists, there is a need in the semiconductor industry for new types of high-performance photoresists.

[0006] To overcome the shortcomings of the chemically amplified organic photosensitive compositions described above, inorganic photosensitive compositions have been studied. Inorganic photosensitive compositions are primarily used for negative tone patterning, which is resistant to removal by developer compositions due to chemical modification by a non-chemically amplified mechanism. Inorganic compositions contain inorganic elements with higher EUV absorption than hydrocarbons, enabling them to maintain sensitivity even through a non-chemically amplified mechanism. They are also known to be less susceptible to stochastic effects, resulting in fewer line edge roughness and fewer defects.

[0007] Inorganic photoresists based on peroxopolyacids of tungsten and tungsten mixed with niobium, titanium, and / or tantalum have been reported for patterning radiation sensitive materials (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 demonstrated using cationic hafnium metal oxide sulfate (HfSOx) materials in combination with a peroxo complexing agent to image 15 nm half-pitch (HP) features by projection EUV lithography (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 demonstrated the best performance of any non-CA photoresist and possessed a photovoltaic speed approaching the requirements for viable EUV photoresists. However, hafnium metal oxide sulfate materials with peroxo complexing agents have several practical drawbacks. First, these materials are coated in a highly corrosive sulfuric acid / hydrogen peroxide mixture, resulting in poor shelf-life stability. Second, as a complex mixture, structural modification for performance improvement is not easily possible. Third, they must be developed in extremely high concentrations, such as 25 wt% tetramethylammonium hydroxide (TMAH) solutions.

[0009] Recently, active research has been conducted on tin-containing molecules that exhibit excellent extreme ultraviolet absorption. Organotin polymers, for example, enable negative-tone patterning that is not removed by organic developers through cross-linking via oxo bonds with surrounding chains, resulting from the dissociation of alkyl ligands by light absorption or the secondary electrons generated by light absorption. These organotin polymers have demonstrated dramatic improvements in sensitivity while maintaining resolution and line edge roughness. However, further improvements in these patterning characteristics are necessary for commercialization.

[0010] One embodiment provides a composition for a semiconductor photoresist having excellent resolution characteristics and pattern adhesion by improving CD (critical dimension) stability by reducing the influence of variables during pattern formation.

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

[0012] A composition for a semiconductor photoresist according to one embodiment includes an organometallic compound, a cyclic organic acid having an electron withdrawing group (EWG), and a solvent.

[0013] A pattern forming method according to another embodiment includes a step of forming an etching target film on a substrate, a step of forming a photoresist film by applying the aforementioned semiconductor photoresist composition on the etching target film, a step of patterning the photoresist film to form a photoresist pattern, and a step of etching the etching target film using the photoresist pattern as an etching mask.

[0014] A pattern formed using a composition for semiconductor photoresist according to an embodiment can achieve excellent resolution by improving CD stability.

[0015] FIG. 1 is a cross-sectional view illustrating a pattern forming method using a composition for semiconductor photoresist according to one embodiment.

[0016] <Explanation of symbols>

[0017] 100: Substrate 102: Thin film

[0018] 104: Resist underlayer 106: Photoresist film

[0019] 106a: Unexposed area 106b: Exposed area

[0020] 108: Photoresist pattern 112: Organic film pattern

[0021] 110: Patterned mask 114: Thin film pattern

[0022]

[0023] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings. However, in describing this disclosure, descriptions of functions or configurations already known will be omitted to clarify the gist of this disclosure.

[0024] To clarify this description, irrelevant parts have been omitted, and identical 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 indicated for convenience of explanation, and therefore this description is not necessarily limited to what is shown.

[0025] To clearly illustrate various layers and regions in the drawings, their thicknesses have been enlarged. Furthermore, for convenience of explanation, the thicknesses of some layers and regions have been exaggerated in the drawings. When a layer, membrane, region, plate, or other part is said to be "over" or "on" another part, this includes not only cases where it is "directly over" another part, but also cases where there is another part in between.

[0026] In the present invention, "substitution" means a hydrogen atom is substituted with deuterium, a halogen group, a hydroxyl 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, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), a C1 to C30 alkyl group, a C1 to It means substituted with a 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 a hydrogen atom is not replaced by another substituent and remains a hydrogen atom.

[0027] As used herein, "alkyl group" means a straight-chain or branched-chain aliphatic hydrocarbon group, unless otherwise defined. The alkyl group may be a "saturated alkyl group" that does not contain any double bond or triple bond.

[0028] 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.

[0029] In this description, “cycloalkyl group” means a monovalent cyclic aliphatic saturated hydrocarbon group, unless otherwise defined.

[0030] The cycloalkyl group may be a C3 to C8 cycloalkyl group, for example, a C3 to C7 cycloalkyl group, or a C3 to C6 cycloalkyl group. For example, the cycloalkyl group may be, but is not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

[0031] As used herein, "aryl group" means a substituent in which all atoms of the cyclic substituent have p-orbitals and these p-orbitals form conjugation, and includes a monocyclic or fused ring polycyclic (i.e., a ring that shares adjacent pairs of carbon atoms) functional groups.

[0032] As used herein, "heteroaryl group" means 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 connected via a sigma bond, or when the heteroaryl group includes 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 include 1 to 3 of the heteroatoms.

[0033] In this specification, unless otherwise defined, “alkenyl group” means an aliphatic unsaturated alkenyl group, which is a straight-chain or branched-chain aliphatic hydrocarbon group containing one or more double bonds.

[0034] In this specification, unless otherwise defined, “alkynyl group” means a straight-chain or branched-chain aliphatic hydrocarbon group, which is an aliphatic unsaturated alkynyl group containing one or more triple bonds.

[0035] A composition for semiconductor photoresist according to the following implementation example is described.

[0036] A composition for a semiconductor photoresist according to one embodiment of the present invention may include an organometallic compound, a cyclic organic acid having an electron withdrawing group (EWG), and a solvent.

[0037] A method for forming a pattern using a composition for a semiconductor photoresist including an organometallic compound comprises the steps of applying a photoresist composition onto a film to be etched, thereby coating the film to be etched with organometallic compounds or cluster molecules thereof in the photoresist composition, and removing organic substances in the photoresist composition and patterning a metal oxide by performing a first baking process, an exposure process, a second baking process, and a development process.

[0038] At this time, the patterning of the metal oxide is affected by various variables such as temperature, solvent, concentration, catalyst, and atmospheric atmosphere, and in particular, the smaller the pattern size, the greater the influence. Typically, in the case of a pattern formed by a photoresist composition containing an organometallic compound, the size is very small, ranging from several nm to several tens of nm, so the influence of process conditions on pattern formation is greater compared to conventional photoresists.

[0039] In particular, it has been found that pattern formation using a photoresist composition containing an organometallic compound is affected by the concentration of nitrogen oxides (NOx) in the atmosphere. NOx is a highly reactive substance present in the atmosphere and can react with atmospheric moisture, sunlight, etc. to cause phenomena such as smog. When the concentration of NOx exceeds a certain level, it has been confirmed that the pattern width confirmed after development differs from the target value.

[0040] Accordingly, in the present invention, a cyclic organic acid having an electron withdrawing group (EWG) is introduced to enable coordination to the central metal of an organometallic compound, thereby reducing the reactivity of the central metal toward radicals and stabilizing the generated radicals to lower the reactivity, thereby developing a photoresist composition capable of suppressing the phenomenon of pattern width deformation caused by NOx.

[0041] The cyclic organic acid may be included in an amount of 0.01 to 5 wt% relative to 100 wt% of the organometallic compound.

[0042] For example, the cyclic organic acid may be included in an amount of 0.05 to 2 wt% relative to 100 wt% of the organometallic compound.

[0043] When the above-mentioned cyclic organic acid is included in the above-mentioned content range, the effect of maintaining pattern formation while suppressing the influence of NOx can be realized.

[0044] For example, the cyclic organic acid having the electron-withdrawing group can be represented by the following chemical formula 1.

[0045] [Chemical Formula 1]

[0046]

[0047] In the above chemical formula 1,

[0048] n is one of the integers 1 to 3,

[0049] 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,

[0050] X is an electron-turning element.

[0051] An electron withdrawing group is a group that itself draws electron density from adjacent atoms by resonance, inductive, hyperconjugation, or a combination thereof, and may include a weak electron withdrawing group, such as a halogen; a moderate electron withdrawing group, such as an aldehyde group, a carbonyl-containing group, a carboxyl group, an ester group, or an amide group; or a strong electron withdrawing group, such as a trihalide group, a cyano group, a sulfone group, a sulfonate group, or a nitro group.

[0052] For example, the electron-withdrawing group may be a halogen, a C1 to C10 haloalkyl group, a cyano group, a cyano-containing group, a nitro group, an ammonium group, an amidino group, a C1 to C10 alkylamine group, a C6 to C20 arylamine group, a C7 to C20 arylalkylamine group, a C1 to C10 carboxyl group, an ester group, a C1 to C10 alkyl group substituted with a carbonyl group, a C2 to C10 heteroalkyl group substituted with a carbonyl group, a C6 to C14 aryl group substituted with a carbonyl group, a C2 to C10 heteroaryl group substituted with a carbonyl group, an amide group, a sulfone group, a sulfonate group, or a C2 to C30 N-containing heteroaryl group.

[0053] As a specific example, the electron-withdrawing group may be a halogen, a C1 to C10 haloalkyl group, a cyano group, a cyano-containing group, a nitro group, an ammonium group, a C1 to C10 carboxyl group, an ester group, a C1 to C10 alkyl group substituted with a carbonyl group, a C2 to C10 heteroalkyl group substituted with a carbonyl group, a C6 to C14 aryl group substituted with a carbonyl group, a C2 to C10 heteroaryl group substituted with a carbonyl group, an amide group, a sulfone group, a sulfonate group, or a C2 to C30 N-containing heteroaryl group.

[0054] As a more specific example, the electron-withdrawing group may be Cl, F, a C1 to C5 fluoroalkyl group, a cyano group, a cyano-containing group, a nitro group, an ammonium group, an amide group, a sulfone group, a sulfonate group, a pyrrolyl group, a pyridyl group, a pyrimidyl group, or a triazinyl group.

[0055] For example, the electron-withdrawing group may be F, a trifluoromethyl group, a cyano group, a nitro group, an ammonium group, a C1 to C6 alkylamine group, a C6 to C12 arylamine group, a C7 to C12 arylalkylamine group, or a sulfonate group.

[0056] In one embodiment, the cyclic organic acid having the electron-withdrawing group is benzoic acid substituted with at least one selected from the group consisting of F, a trifluoromethyl group, a cyano group, a nitro group, an ammonium group, an alkylamine group of C1 to C6, an arylamine group of C6 to C12, an arylalkylamine group of C7 to C12, and a sulfonate group; or

[0057] It may be a cyclohexyl carboxylic acid substituted with at least one selected from the group consisting of F, a trifluoromethyl group, a cyano group, a nitro group, an ammonium group, an alkylamine group having C1 to C6, an arylamine group having C6 to C12, an arylalkylamine group having C7 to C12, and a sulfonate group.

[0058] For example, cyclic organic acids having the electron-withdrawing group include 2-nitrobenzoic acid, 3-nitrobenzoic acid, 4-trifluoromethyl benzoic acid, 3,5-dinitrobenzoic acid, and 2,4-dinitrobenzoic acid.

[0059] In this specification, a C3 to 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 to C20 non-aromatic carbocyclic group may be a monocyclic group or a polycyclic group.

[0060] In this specification, a C6 to C30 aromatic carbocyclic group refers to an aromatic ring having 6 to 20 carbon atoms as ring-forming atoms. Examples thereof include, but are not limited to, a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, and a chrysene group.

[0061] The above non-aromatic carbocyclic group and aromatic carbocyclic group can be modified in various ways, such as being a divalent group, a trivalent group, or a tetravalent group, depending on the number of connected substituents.

[0062] The cyclic organic acid having the electron-withdrawing group may be included in the composition for semiconductor photoresist at 1 ppm to 1,200 ppm.

[0063] For example, the cyclic organic acid having the electron-withdrawing group may be included in the composition for semiconductor photoresists at 5 to 800 ppm, 10 to 800 ppm, 20 to 800 ppm, or 50 to 600 ppm.

[0064] The above organometallic compound may be included in an amount of 0.5 wt% to 30 wt% based on 100 wt% of the composition for semiconductor photoresist.

[0065] According to one embodiment, a composition for a semiconductor photoresist can improve the sensitivity of a photoresist by including the organometallic compound and the cyclic organic acid having the electron-withdrawing group in the above content range.

[0066] The above organometallic compound may be an organotin compound containing at least one of an organooxy group and an organocarbonyloxy group.

[0067] The above organometallic compound can be represented by the following chemical formula 2.

[0068] [Chemical Formula 2]

[0069]

[0070] In the above chemical formula 2,

[0071] R 1 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 C6 to C30 arylalkyl group,

[0072] R 2 Inland R 4 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 C6 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(CO)R c , R c is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), alkylamido or dialkylamido (-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) or a thiocarboxyl group (-S(CO)R l , R lis 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,

[0073] R 2 Inland R 4 At least one of 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(CO)R c , R c is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), alkylamido or dialkylamido (-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 gare each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), amidinato (-NR g C(NR h )R i , 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.

[0074] The above R 2 Inland R 4 At least one of alkoxy and aryloxy (-OR b , where R ais 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(CO)R c , R c may be 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.

[0075] Meanwhile, the compound represented by the above chemical formula 2 has -OR as a ligand b or -OC(=O)R c By including it, a pattern formed using a semiconductor photoresist composition including it can exhibit excellent limit resolution.

[0076] Also, -OR b or -OC(=O)R c The ligand can determine the solubility of the compound represented by the above chemical formula 2 in a solvent.

[0077] The above R 1 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 bonds 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,

[0078] 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,

[0079] 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.

[0080] The above R 1 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 butainyl 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,

[0081] 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 propynyl group, a buthanyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, or a combination thereof,

[0082] R cmay be 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 ethanyl group, a propynyl group, a buthanyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, or a combination thereof.

[0083] In addition, the Sn-containing organometallic compound may be represented by the following chemical formula 3 or chemical formula 4.

[0084] [Chemical Formula 3]

[0085] R 5 z SnO (2-(z / 2)-(x / 2)) (OH) x

[0086] In the above chemical formula 3,

[0087] R 5 is a C1 to C31 hydrocarbyl group, wherein 0 < z ≤ 2 and 0 < (z+x) ≤ 4;

[0088] [Chemical Formula 4]

[0089] R 6 a M b X c Y d

[0090] In the above chemical formula 4,

[0091] R 6 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,

[0092] M is tin (Sn) or antimony (Sb),

[0093] X is sulfur (S), selenium (Se), or tellurium (Te),

[0094] Y is -OR m or -OC(=O)R n And,

[0095] The above 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,

[0096] 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,

[0097] The above a, b, c and d are each independently integers from 1 to 20.

[0098] The solvent included in the composition for semiconductor photoresist according to one embodiment may be an organic solvent, and may include, but is 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), mixtures thereof, and the like.

[0099] A composition for a semiconductor resist according to one embodiment may further include a resin in addition to the above-described organometallic compound, polymer additive, and solvent.

[0100] The above resin may be a phenolic resin containing at least one aromatic moiety listed in Group 1 below.

[0101] [Group 1]

[0102]

[0103] The above resin may have a weight average molecular weight of 500 to 20,000.

[0104] The above resin may be included in an amount of 0.1 wt% to 50 wt% based on the total content of the composition for the semiconductor photoresist.

[0105] When the above resin is contained in the above content range, it can have excellent etch resistance and heat resistance.

[0106] Meanwhile, it is preferable that the composition for the semiconductor photoresist is composed of the above-described organometallic compound, cyclic organic acid, solvent, and resin.

[0107] The composition for semiconductor photoresist according to the above-described embodiment may further include additives, if necessary. Examples of the additives include surfactants, cross-linking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0108] Surfactants may include, but are not limited to, alkylbenzenesulfonic acid salts, alkylpyridinium salts, polyethylene glycols, quaternary ammonium salts, or combinations thereof.

[0109] Examples of the crosslinking agent include, but are not limited to, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, an acrylic-based crosslinking agent, an epoxy-based crosslinking agent, or a polymer-based crosslinking agent. As a crosslinking agent having at least two crosslinking-forming substituents, for example, compounds such as 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-cyclohexane dicarboxylate, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea can be used.

[0110] The leveling agent is used to improve the coating flatness during printing, and any commercially available, publicly known leveling agent can be used.

[0111] The organic acid may be, but is not limited to, p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, a fluorinated sulfonium salt, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or a combination thereof.

[0112] The quencher may be diphenyl(p-tolyl)amine, methyl diphenyl amine, triphenyl amine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0113] The amount of these additives used can be easily adjusted according to the desired properties and may be omitted.

[0114] In addition, the semiconductor photoresist composition may further use a silane coupling agent as an additive as an adhesion promoter to improve adhesion to a substrate (e.g., to improve adhesion of the semiconductor photoresist composition to a substrate). The silane coupling agent may be, but is not limited to, a carbon-carbon unsaturated bond-containing silane compound such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryl trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; or trimethoxy[3-(phenylamino)propyl]silane.

[0115] The above composition for semiconductor photoresist can form a pattern having a high aspect ratio without causing pattern collapse. Therefore, for example, a photoresist process using light having a wavelength of 5 nm to 150 nm, for example, a photoresist process using light having a wavelength of 5 nm to 100 nm, for example, a photoresist process using light having a wavelength of 5 nm to 80 nm, for example, a photoresist process using light having a wavelength of 5 nm to 50 nm, for example, a photoresist process using light having a wavelength of 5 nm to 80 nm, for example, a photoresist process using light having a wavelength of 5 nm to 50 nm, for example, a photoresist process using light having a wavelength of 5 nm to 30 nm, for example, a photoresist process using light having a wavelength of 5 nm to 30 nm, for example, a photoresist process using light having a wavelength of 5 nm to 20 nm, for example, For example, it can be used in a photoresist process using light with a wavelength of 5 nm to 20 nm. Therefore, by using the composition for semiconductor photoresist according to one embodiment, extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5 nm can be implemented.

[0116] Meanwhile, according to another embodiment, a method for forming a pattern using the above-described semiconductor photoresist composition may be provided. For example, the pattern formed may be a photoresist pattern.

[0117] Another embodiment of the method for forming a pattern includes the steps of forming an etching target film on a substrate, applying the aforementioned semiconductor photoresist composition on the etching target film to form a photoresist film, patterning the photoresist film to form a photoresist pattern, and etching the etching target film using the photoresist pattern as an etching mask.

[0118] Hereinafter, a method for forming a pattern using the above-described semiconductor photoresist composition will be described with reference to FIG. 1. FIG. 1 is a cross-sectional view illustrating a method for forming a pattern using the semiconductor photoresist composition according to the present invention.

[0119] Referring to (a) of Fig. 1, first, an etching target is prepared. An example of the etching target may be a thin film (102) formed on a semiconductor substrate (100). The following description will be limited to the case where the etching target is a thin film (102). The surface of the thin film (102) is cleaned to remove contaminants remaining on the thin film (102). The thin film (102) may be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film.

[0120] Next, a composition for forming a resist underlayer film (104) is coated on the surface of the cleaned thin film (102) by applying a spin coating method. However, one embodiment is not necessarily limited thereto, and various known coating methods, for example, spray coating, dip coating, knife edge coating, printing methods such as inkjet printing and screen printing, etc. may be used.

[0121] The above resist underlayer coating process can be omitted, and the following describes a case where the resist underlayer is coated.

[0122] Thereafter, a drying and baking process is performed to form a resist underlayer film (104) on the thin film (102). The baking process is performed at about 100 to about 500°C, and may be performed at about 100 to about 300°C, for example.

[0123] The resist underlayer film (104) is formed between the substrate (100) and the photoresist film (106), so that when the radiation reflected from the interface or interlayer hardmask of the substrate (100) and the photoresist film (106) is scattered into an unintended photoresist region, it can prevent the unevenness of the photoresist linewidth and the interference with the pattern formation.

[0124] Referring to (b) of FIG. 2, the semiconductor photoresist composition described above is coated on the resist underlayer film (104) to form a photoresist film (106). The photoresist film (106) may be in the form of a thin film (102) formed on a substrate (100) coated with the semiconductor photoresist composition described above and then cured through a heat treatment process.

[0125] More specifically, the step of forming a pattern using a composition for semiconductor photoresist may include a step of applying the above-described composition for semiconductor photoresist onto a substrate (100) on which a thin film (102) is formed by spin coating, slit coating, inkjet printing, etc., and a step of drying the applied composition for semiconductor photoresist to form a photoresist film (106).

[0126] Since the composition for semiconductor photoresist has already been described in detail, a duplicate description will be omitted.

[0127] 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.

[0128] Referring to (c) of Fig. 1, the photoresist film (106) is selectively exposed using a patterned mask (110).

[0129] For example, examples of light that can be used in the above exposure process include light having an activating irradiance of i-line (wavelength 365 nm), a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), and light having a high-energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0130] More specifically, the exposure light according to one embodiment may be 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).

[0131] The exposed area (106b) of the photoresist film (106) forms a polymer through a cross-linking reaction such as condensation between organometallic compounds, and thus has a different solubility from the unexposed area (106a) of the photoresist film (106).

[0132] 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 area (106b) of the photoresist film (106) becomes difficult to dissolve in a developer.

[0133] In (d) of Fig. 1, a photoresist pattern (108) is illustrated that is formed by dissolving and removing the photoresist film (106a) corresponding to the unexposed area using a developer. Specifically, the photoresist pattern (108) corresponding to the negative tone image is completed by dissolving and then removing the photoresist film (106a) corresponding to the unexposed area using an organic solvent such as 2-heptanone.

[0134] As described above, the developer used in the pattern forming method according to one embodiment may be an organic solvent. Examples of the organic solvent used in the pattern forming method according to one 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; or combinations thereof.

[0135] However, the photoresist pattern according to one embodiment is not necessarily limited to being formed as a negative tone image, and may also be formed to have a positive tone image. In this case, a developer that can be used to form a positive tone image may include a quaternary ammonium hydroxide composition such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or a combination thereof.

[0136] 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), or light having high energy such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam) may have a width of 5 nm to 100 nm. For example, the photoresist pattern (108) may be formed to 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.

[0137] Meanwhile, the photoresist pattern (108) may have a pitch having a half-pitch of about 50 nm or less, for example, 40 nm or less, for example, 30 nm or less, for example, 20 nm or less, for example, 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.

[0138] Next, the resist underlayer film (104) is etched using the photoresist pattern (108) as an etching mask. An organic film pattern (112) is formed through the etching process described above. The formed organic film pattern (112) may also have a width corresponding to the photoresist pattern (108).

[0139] Referring to (e) of Fig. 1, the photoresist pattern (108) is applied 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).

[0140] The etching of the above thin film (102) can be performed by dry etching using, for example, an etching gas, and the etching gas can be, for example, CHF3, CF4, Cl2, BCl3, and a mixed gas thereof.

[0141] In the previously performed exposure process, the thin film pattern (114) formed using the photoresist pattern (108) formed by the exposure process performed using the EUV light source may have a width corresponding to the photoresist pattern (108). For example, it may have a width of 5 nm to 100 nm, similar to the photoresist pattern (108). For example, the thin film pattern (114) formed by the exposure process performed using the 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, 5 nm to 20 nm, similar to the photoresist pattern (108), and more specifically, it may be formed with a width of 20 nm or less.

[0142] Hereinafter, the present invention will be described in more detail through examples relating to the preparation of the semiconductor photoresist composition described above. However, the technical features of the present invention are not limited by the following examples.

[0143]

[0144] Synthesis of organometallic compounds

[0145] Synthesis Example 1

[0146] Add 340.7g of t-butylSnPh and 300g of propionic acid to a 250ml two-neck round-bottom flask and heat under reflux for 24 hours.

[0147] Unreacted propionic acid is removed under reduced pressure to obtain a compound represented by the following chemical formula 5.

[0148] [Chemical Formula 5]

[0149]

[0150]

[0151] Synthesis Example 2

[0152] Add 30 ml of anhydrous pentane to 310 g of t-AmylSnCl, maintain the temperature at 0°C, then add 7.4 g of diethylamine and 6.1 g of ethanol, and stir at room temperature for 1 hour. When the reaction is complete, filter, concentrate, and dry under vacuum to obtain a compound represented by the following chemical formula 6.

[0153] [Chemical Formula 6]

[0154]

[0155]

[0156] (Manufacture of composition for semiconductor photoresist)

[0157] Examples 1 to 8 and Comparative Examples 1 to 6

[0158] The organometallic compounds represented by chemical formulas 5 and 6 obtained in Synthesis Examples 1 and 2 were dissolved in Propylene glycol methyl ether acetate (PGMEA) at a concentration of 3%, and cyclic organic acids C1 to C5 were added and dissolved at the concentrations shown in Table 1 below, and then filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to prepare a composition for semiconductor photoresists according to Examples and Comparative Examples. The composition was coated on a silicon wafer to a thickness of 240 Å, and then a patterned film was prepared through PAB, exposure, PEB, and development processes.

[0159] Organometallic compound (wt%)Cyclic organic acid (ppm)Example 1Chemical formula 5(3.00)C3(100)Example 2C4(100)Example 3C5(100)Example 4C3(500)Comparative example 1--Comparative example 2C1(100)Comparative example 3C2(100)Comparative example 4C2(500)Comparative example 5C3(1,600)Example 5Chemical formula 6(3.00)C3(100)Example 6C4(100)Example 7C5(100)Example 8C3(500)

[0160] C1: Benzoic acid

[0161] C2: 4-methyl benzoic acid

[0162] C3: 3-nitro benzoic acid

[0163] C4: 4-trifluoromethyl benzoic acid

[0164] C5: 3,5-dinitrobenzoic acid

[0165]

[0166] Evaluation: CD uniformity and pattern adhesion evaluation

[0167] The resist compositions for semiconductors according to Examples 1 to 8 and Comparative Examples 1 to 6 were spin-coated at 1500 rpm for 30 seconds on a 200 mm circular silicon wafer, and then heated at a temperature of 110° C. for 60 seconds.

[0168] Afterwards, a linear array with a line width of 180 nm was projected onto the wafer coated with the photoresist composition using KrF light. The resist and substrate were then heated on a hot plate at 180°C for 120 seconds. The fired film was developed with PGMEA solvent to form a negative tone image. Finally, firing was performed at 200°C for 180 seconds to complete the process.

[0169] Using CD-SEM, the CD values ​​for each resist were measured when there was no NOx in the atmosphere and when the NOx concentration was 0.01 ppm or higher, and the CD change (ΔCD(%)) is shown in Table 2 below. The NOx concentration was measured using a Sky2000-NOx detector (Safe Gas). The formula for calculating the change is as follows.

[0170] [ceremony]

[0171] ΔCD% = (CD ≥0.01ppm NOx / CD w / o NOx )

[0172]

[0173] In addition, for the pattern image formed above through CD-SEM, if any part of the pattern was separated or disappeared within the 15㎛ x 15㎛ area, it was judged as 'X', and if all of the pattern was present, it was judged as '○', and the results are shown in Table 2 below.

[0174] CD Uniformity (%) Pattern Adhesion Example 15○ Example 210○ Example 33○ Example 43○ Example 520○ Example 625○ Example 720○ Example 820○ Comparative Example 160○ Comparative Example 2100○ Comparative Example 355○ Comparative Example 4 Not measurable X Comparative Example 5 Not measurable X

[0175] From the results in Table 2, it can be confirmed that the patterns formed using the semiconductor photoresist compositions according to Examples 1 to 8 have excellent resistance to NOx influence compared to Comparative Examples 1 to 3 and thus excellent pattern uniformity, and that the pattern adhesion is also excellent compared to Comparative Examples 4 and 5.

[0176]

[0177] While specific embodiments of the present invention have been described and illustrated above, it will be apparent to those skilled in the art that the present invention is not limited to the described embodiments, and that various modifications and variations can be made without departing from the spirit and scope of the present invention. Accordingly, such modifications or variations should not be understood individually from the technical spirit or perspective of the present invention, and such modified embodiments should fall within the scope of the claims of the present invention.

Claims

1. Organometallic compounds; Cyclic organic acids having electron withdrawing groups (EWG); and Contains a solvent, A composition for a semiconductor photoresist, comprising 0.01 to 5 wt% of the cyclic organic acid relative to the organometallic compound.

2. In paragraph 1, A composition for a semiconductor photoresist, comprising 0.05 to 2 wt% of the cyclic organic acid relative to 100 wt% of the organometallic compound.

3. In paragraph 1, A composition for a semiconductor photoresist, wherein the cyclic organic acid having the electron-withdrawing group is represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, n is one of the integers 1 to 3, 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, X is an electron-turning element.

4. In paragraph 3, A composition for a semiconductor photoresist, wherein the 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.

5. In paragraph 1, A composition for a semiconductor photoresist, wherein the electron-withdrawing group is a halogen, a C1 to C10 haloalkyl group, a cyano group, a cyano-containing group, a nitro group, an ammonium group, an amidino group, a C1 to C10 alkylamine group, a C6 to C20 arylamine group, a C7 to C20 arylalkylamine group, a C1 to C10 carboxyl group, an ester group, a C1 to C10 alkyl group substituted with a carbonyl group, a C2 to C10 heteroalkyl group substituted with a carbonyl group, a C6 to C14 aryl group substituted with a carbonyl group, a C2 to C10 heteroaryl group substituted with a carbonyl group, an amide group, a sulfone group, a sulfonate group, or a C2 to C30 N-containing heteroaryl group.

6. In paragraph 1, A composition for a semiconductor photoresist, wherein the electron-withdrawing group is F, a trifluoromethyl group, a cyano group, a nitro group, an ammonium group, a C1 to C6 alkylamine group, a C6 to C12 arylamine group, a C7 to C12 arylalkylamine group, or a sulfonate group.

7. In paragraph 1, The cyclic organic acid having the above electron-withdrawing group is Benzoic acid substituted with at least one selected from the group consisting of F, trifluoromethyl group, cyano group, nitro group, ammonium group, C1 to C6 alkylamine group, C6 to C12 arylamine group, C7 to C12 arylalkylamine group and sulfonate group; or A composition for a semiconductor photoresist, which is a cyclohexyl carboxylic acid substituted with at least one selected from the group consisting of F, a trifluoromethyl group, a cyano group, a nitro group, an ammonium group, a C1 to C6 alkylamine group, a C6 to C12 arylamine group, a C7 to C12 arylalkylamine group, and a sulfonate group.

8. In paragraph 1, A composition for a semiconductor photoresist, wherein the cyclic organic acid having the electron-withdrawing group is contained in an amount of 1 ppm to 1,200 ppm based on 100 wt% of the composition for a semiconductor photoresist.

9. In paragraph 1, A composition for a semiconductor photoresist further comprising an additive of a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher or a combination thereof.

10. In paragraph 1, A composition for a semiconductor photoresist, wherein the above organometallic compound is an organotin compound containing at least one of an organooxy group and an organocarbonyloxy group.

11. In paragraph 1, The above organic metal compound is a composition for a semiconductor photoresist represented by the following chemical formula 2: [Chemical Formula 2] In the above chemical formula 2, R 1 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 2 Inland R 4 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(CO)R c , R c is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), alkylamido or dialkylamido (-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 (-S(CO)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 2 Inland R 4 At least one of 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(CO)R c , R c is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), alkylamido or dialkylamido (-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 g C(NR h )R i , 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.

12. In paragraph 11, The above R 2 Inland R 4 At least one of 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(CO)R c , R c A composition for a semiconductor photoresist, wherein the compound 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.

13. In paragraph 12, The above R 1 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 bonds 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 A composition for a semiconductor photoresist, wherein the composition comprises 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.

14. In paragraph 1, The above organic metal compound is a composition for a semiconductor photoresist represented by the following chemical formula 3 or chemical formula 4: [Chemical Formula 3] R 5 z SnO (2-(z / 2)-(x / 2)) (OH) x In the above chemical formula 3, R 5 is a C1 to C31 hydrocarbyl group, wherein 0 < z ≤ 2 and 0 < (z+x) ≤ 4; [Chemical Formula 4] R 6 a M b X c Y d In the above chemical formula 4, R 6 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, M is tin (Sn) or antimony (Sb), X is sulfur (S), selenium (Se), or tellurium (Te), Y is -OR m or -OC(=O)R n And, The above 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 above a, b, c and d are each independently integers from 1 to 20.

15. Step of forming an etching target film on a substrate; A step of forming a photoresist film by applying a semiconductor photoresist composition according to any one of claims 1 to 14 on the etching target film; A step of forming a photoresist pattern by patterning the photoresist film; and A pattern forming method comprising a step of etching the etching target film using the photoresist pattern as an etching mask.

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