Composition for semiconductor photoresist and pattern forming method using same

Abstract

To provide a composition for semiconductor photoresist that has superior sensitivity and resolution characteristics, enhanced solubility in developer, and improved against moisture, and a pattern forming method using the same.SOLUTION: The present invention relates to a composition for semiconductor photoresist comprising: an organometallic compound; a polymer additive including a structural unit represented by the following Chemical Formula 1; and a solvent, and a pattern forming method using the same. The details of Chemical Formula 1 are described in the specification.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] EUV (extreme ultraviolet) lithography is attracting attention as one of the elemental technologies for manufacturing next-generation semiconductor devices. EUV lithography is a pattern formation technology that uses EUV light with a wavelength of 13.5 nm as the exposure light source. It has been demonstrated that EUV lithography can form extremely fine patterns (e.g., 20 nm or less) during the exposure step in the semiconductor device manufacturing process.

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

[0004] Intrinsic image blur due to acid-catalyzed reactions in such polymeric photoresists limits resolution at small feature sizes, a long-known fact in electron beam (e-beam) lithography. Chemically amplified (CA) photoresists, designed for high sensitivity, can experience additional difficulties under EUV exposure, in part because their typical elemental makeup reduces the photoresist's absorbance at 13.5 nm wavelengths, thereby reducing sensitivity.

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

[0006] To overcome the drawbacks of the chemically amplified organic photosensitive compositions described above, inorganic photosensitive compositions have been developed. Inorganic photosensitive compositions are primarily used in negative-tone patterning, where they are resistant to removal by developer compositions due to chemical modification through a non-chemically amplified mechanism. Inorganic compositions contain inorganic elements with higher EUV absorption than hydrocarbons, ensuring sensitivity even in non-chemically amplified mechanisms. They are also known to have reduced sensitivity to the stochastic effect, resulting in fewer line edge roughness and fewer defects.

[0007] Inorganic photoresists based on peroxopolyacids of tungsten and tungsten mixed with niobium, titanium, and / or tantalum have been reported for patterning radiation-sensitive materials (US Pat. No. 5,061,599; H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298-300, 1986).

[0008] These materials have been effective for patterning large features in bilayer configurations with deep UV, x-ray, and electron beam sources. More recently, impressive performance has been demonstrated when using cationic hafnium metal oxide sulfate (HfSOx) materials with peroxocomplexing agents to image 15 nm half-pitch (HP) patterns with projection EUV exposure (US 2011-0045406; J.K. Stowers, A. Telecky, M. Kocsis, B.L. Clark, D.A. Keszler, A. Grenville, C.N. Anderson, P.P. Naulleau, Proc. SPIE, 7969, 796915, 2011). This system exhibits the best performance of any non-CA photoresist and has photospeeds approaching the requirements for a viable EUV photoresist. However, hafnium metal oxide sulfate materials with peroxo complexing agents have several practical drawbacks. First, these materials are coated with a highly corrosive sulfuric acid / hydrogen peroxide mixture, resulting in poor shelf-life stability. Second, because they are complex mixtures, it is difficult to modify their structure to improve performance. Third, they must be developed using extremely high-concentration solutions, such as 25 wt% TMAH (tetramethylammonium hydroxide).

[0009] Recently, active research has been conducted on tin-containing molecules due to their excellent absorption of extreme ultraviolet light. In the case of organotin polymers, one such polymer, alkyl ligands are dissociated by light absorption or the secondary electrons generated by the absorption, and crosslinking with surrounding chains through oxo bonds enables negative-tone patterning that is resistant to removal by organic developers. These organotin polymers have demonstrated dramatic improvements in sensitivity while maintaining resolution and line edge roughness, but further improvements in their patterning properties are required for commercialization. Summary of the Invention [Problem to be solved by the invention]

[0010] An embodiment of the present invention provides a composition for semiconductor photoresist, which has excellent sensitivity and resolution characteristics, improved solubility in a developer, and improved stability against moisture.

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

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

[0013] A method for forming a pattern according to another embodiment of the present invention includes forming a layer to be etched on a substrate; applying the above-described semiconductor photoresist composition on the layer to be etched to form a photoresist layer; patterning the photoresist layer to form a photoresist pattern; and etching the layer to be etched using the photoresist pattern as an etching mask. [Effects of the Invention]

[0014] A pattern formed using the semiconductor photoresist composition according to one embodiment of the present invention has excellent sensitivity and resolution, and can also have improved stability against moisture. [Brief explanation of the drawings]

[0015] [Figure 1] 1A to 1C are cross-sectional views illustrating a method for forming a pattern using a semiconductor photoresist composition according to an embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0016] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, in the description, descriptions of functions or configurations that are already known will be omitted in order to clarify the gist of the description.

[0017] In order to clarify the present description, parts unnecessary for the description have been omitted, and the same or similar components have been given the same reference numerals throughout the specification. Furthermore, the size and thickness of each component shown in the drawings are arbitrarily shown for the convenience of explanation, and the present description is not necessarily limited to those shown in the drawings.

[0018] In the drawings, thicknesses of multiple layers and regions are exaggerated to clearly show them. Also, for ease of explanation, the thicknesses of some layers and regions are exaggerated in the drawings. When a layer, film, region, plate, or other portion is said to be "on" another portion, this does not only mean that it is "directly on" that other portion, but also includes the case where there is another portion between them.

[0019] In this description, "substituted" means that a hydrogen atom is replaced with a deuterium atom, a halogen group, a hydroxy group, a carboxyl group, a thiol group, a cyano group, a nitro group, -NRR' (wherein R and R' are each independently hydrogen, a substituted or unsubstituted saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted saturated or unsaturated alicyclic hydrocarbon group having 3 to 30 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms), -SiRR'R'' (wherein R, R', and R'' are each independently hydrogen, a substituted or unsubstituted "Unsubstituted" means that the hydrogen atoms are not substituted with other substituents and remain as hydrogen atoms.

[0020] As used herein, unless otherwise defined, the term "alkyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0021] The alkyl group may be an alkyl group having 1 to 8 carbon atoms. For example, the alkyl group may be an alkyl group having 1 to 7 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. For example, the alkyl group having 1 to 5 carbon atoms may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or a 2,2-dimethylpropyl group.

[0022] In this description, unless otherwise defined, the term "cycloalkyl group" refers to a monovalent cyclic aliphatic saturated hydrocarbon group.

[0023] The cycloalkyl group may be a cycloalkyl group having 3 to 8 carbon atoms, for example, a cycloalkyl group having 3 to 7 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 3 to 5 carbon atoms, or a cycloalkyl group having 3 to 4 carbon atoms. For example, the cycloalkyl group may be, but is not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

[0024] As used herein, "aliphatically unsaturated organic group" refers to a hydrocarbon group containing bonds between carbon atoms in the molecule that are double bonds, triple bonds, or a combination thereof.

[0025] The aliphatic unsaturated organic group may be an aliphatic unsaturated organic group having 2 to 8 carbon atoms. For example, the aliphatic unsaturated organic group may be an aliphatic unsaturated organic group having 2 to 7 carbon atoms, an aliphatic unsaturated organic group having 2 to 6 carbon atoms, an aliphatic unsaturated organic group having 2 to 5 carbon atoms, or an aliphatic unsaturated organic group having 2 to 4 carbon atoms. For example, the aliphatic unsaturated organic group having 2 to 4 carbon atoms 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-1-propynyl 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.

[0026] As used herein, the term "aryl group" refers to a cyclic substituent in which all elements have p-orbitals and these p-orbitals form conjugation, including monocyclic or fused-ring polycyclic (i.e., rings that share adjacent pairs of carbon atoms) functional groups.

[0027] As used herein, the term "heteroaryl group" refers to an aryl group containing at least one heteroatom selected from the group consisting of N, O, S, P, and Si. Two or more heteroaryl groups may be directly linked via a sigma bond, or, if the heteroaryl group contains two or more rings, the two or more rings may be fused to each other. If the heteroaryl group is a fused ring, each ring may contain 1 to 3 heteroatoms.

[0028] As used herein, unless otherwise defined, the term "alkenyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group and an aliphatic unsaturated alkenyl group containing one or more double bonds.

[0029] As used herein, unless otherwise defined, the term "alkynyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group and an aliphatic unsaturated alkynyl group containing one or more triple bonds.

[0030] Hereinafter, a semiconductor photoresist composition according to one embodiment will be described.

[0031] A composition for semiconductor photoresist according to an embodiment of the present invention may include an organometallic compound, a polymer additive including a structural unit represented by the following Formula 1, and a solvent. [ka]

[0032] In the above Chemical Formula 1, R 1 is hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, R 2 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, including a trifluoromethyl group and a hydroxy group, R 3 ~R 6are each independently hydrogen, fluorine, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a combination thereof; n1 and n2 each independently represent an integer from 0 to 10; n1+n2 is equal to or greater than 1, X 1 is a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, -(CO)O-, -O(CO), -O(CO)O-, -NR a -(where R a is hydrogen, deuterium, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), or a combination thereof; * indicates a connection point.

[0033] The polymer additive contained in the semiconductor photoresist composition contains fluorine, which improves sensitivity and LER. In particular, due to the hydrophobicity of fluorine, it has an excellent effect of reducing defects and can improve stability against moisture.

[0034] Furthermore, by including an alkylene chain in the structural unit, the solubility in a developer can be improved.

[0035] As an example, the above-mentioned R 2 may be an alkyl group having 1 to 20 carbon atoms substituted with at least one trifluoromethyl group and at least one hydroxy group.

[0036] As a specific example, the R 2 may be an alkyl group having 1 to 20 carbon atoms substituted with at least two trifluoromethyl groups and at least one hydroxy group.

[0037] For example, the R 2 may be an alkyl group having 1 to 20 carbon atoms substituted with two trifluoromethyl groups and one hydroxy group.

[0038] In one embodiment, the R 2may be an alkyl group having 1 to 10 carbon atoms substituted with two trifluoromethyl groups and one hydroxy group.

[0039] In a specific embodiment, the R 2 may be an alkyl group having 1 to 5 carbon atoms substituted with two trifluoromethyl groups and one hydroxy group.

[0040] In a more specific embodiment, the R 2 may be an alkyl group having 1 to 3 carbon atoms substituted with two trifluoromethyl groups and one hydroxy group.

[0041] In a most specific embodiment, the R 2 may be a methyl group substituted with two trifluoromethyl groups and one hydroxy group.

[0042] For example, Chemical Formula 1 is represented by Chemical Formula 1-1 below. [ka]

[0043] In the above chemical formula 1-1, R 1 is hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, R 3 ~R 6 are each independently hydrogen, fluorine, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a combination thereof; n1 and n2 each independently represent an integer from 0 to 10; n1+n2 is equal to or greater than 1, X 1 is a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, -(CO)O-, -O(CO), -O(CO)O-, -NR a -(where R a is hydrogen, deuterium, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), or a combination thereof; * indicates a connection point.

[0044] If n1 is 2 or more, each R 3 may be the same or different from each other.

[0045] If n1 is 2 or more, each R 4 may be the same or different from each other.

[0046] If n2 is 2 or more, each R 5 may be the same or different from each other.

[0047] If n2 is 2 or more, each R 6 may be the same or different from each other.

[0048] As a specific example, the structural unit represented by Chemical Formula 1 may be one selected from the structural units listed in Group 1 below. [ka]

[0049] In Group 1, R 1 are each independently hydrogen or a methyl group; * indicates a connection point.

[0050] The polymer additive containing the structural unit represented by Chemical Formula 1 may be included in an amount of 0.001 to 10 wt % relative to 100 wt % of the semiconductor photoresist composition.

[0051] For example, the polymer additive containing the structural unit represented by Chemical Formula 1 may be included in an amount of 0.01 to 10 wt %, 0.01 to 5 wt %, 0.05 to 5 wt %, or 0.1 to 5 wt % relative to 100 wt % of the semiconductor photoresist composition.

[0052] The organometallic compound may be contained in an amount of 0.5% by weight to 30% by weight relative to 100% by weight of the composition for semiconductor photoresist.

[0053] The composition for semiconductor photoresist according to one embodiment includes the organometallic compound and the polymer additive having the structural unit represented by Formula 1 in the above content ranges, thereby improving the sensitivity of the photoresist.

[0054] According to one embodiment, a semiconductor photoresist composition may contain the organometallic compound and a polymer additive having a structural unit represented by Chemical Formula 1 in a weight ratio of 99:1 to 60:40. For example, a semiconductor photoresist composition may contain the organometallic compound and a polymer additive having a structural unit represented by Chemical Formula 1 in a weight ratio of 90:10 to 60:40.

[0055] When the weight ratio of the organometallic compound to the polymer additive satisfies the above range, a semiconductor photoresist composition having excellent sensitivity can be provided.

[0056] The organometallic compound may be an organotin compound containing at least one of an organic oxy group and an organic carbonyloxy group.

[0057] The organometallic compound is represented by the following chemical formula 2. [ka]

[0058] In the above Chemical Formula 2, R 9 is selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms; R 10 ~R12 are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, an alkoxy group, and an aryloxy group (-OR b , where R b is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), a carboxyl group (-O(CO)R c , R c is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, or an unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylamide or dialkylamide (-NR d R e , where R d and R e are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), an amidato (-NR f (COR g ), where R f and R gare each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), amidinato (-NR h C(NR i )R j , where R h , R i and R j are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylthio and arylthio (-SR k , where R k is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof) or a thiocarboxyl group (-S(CO)R l , R l is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; R 10 ~R 12 At least one of the alkoxy and aryloxy (-OR b , where R bis a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), a carboxyl group (-O(CO)R c , R c is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylamide or dialkylamide (-NR d R e , where R d and R e are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), an amidato (-NR f (COR g ), where R f and R g are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), amidinato (-NR h C(NR i )R j , where R h , R i and R jare each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylthio and arylthio (-SR k , where R k is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof) and a thiocarboxyl group (-S(CO)R l , R l is selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof).

[0059] R 10 ~R 12 At least one of the alkoxy and aryloxy (-OR b , where R b is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), and a carboxyl group (-O(CO)R c , R ccan be selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof).

[0060] Meanwhile, the compound represented by Formula 2 contains -OR as a ligand. b or -OC(=O)R c By including the compound (I), a pattern formed using a semiconductor photoresist composition containing the compound can exhibit excellent limit resolution.

[0061] Also, -OR b or -OC(=O)R c The ligand can determine the solubility of the compound represented by Chemical Formula 2 in a solvent.

[0062] R 9 is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted aliphatic unsaturated organic group having 2 to 8 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 4 to 20 carbon atoms, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof; R b is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 8 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof; R cmay be hydrogen, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 8 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof.

[0063] R 9 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 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 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 c may 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 a combination thereof.

[0064] The Sn-containing organometallic compound is represented by the following Chemical Formula 3 or 4. [ka] In the above Chemical Formula 3, R 13is a hydrocarbyl group having 1 to 31 carbon atoms, <z≦2であり、0<(z+x)≦4であり; [ka] In the above Chemical Formula 4, R 14 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated organic group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 4 to 30 carbon atoms, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof; X is sulfur (S), selenium (Se), or tellurium (Te); Y is -OR m or -OC(=O)R n and R m is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; R n is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; The a, b, c, and d are each independently an integer of 1 to 20.

[0065] The solvent included in the semiconductor photoresist composition according to an embodiment may be an organic solvent, and examples thereof may include, but are not limited to, aromatic compounds (e.g., xylene, toluene), alcohols (e.g., 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropyl alcohol, 1-propanol), ethers (e.g., anisole, tetrahydrofuran), esters (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate), ketones (e.g., methyl ethyl ketone, 2-heptanone), and mixtures thereof.

[0066] The semiconductor resist composition according to an embodiment may further include a resin in addition to the organometallic compound, polymer additive, and solvent.

[0067] The resin may be a phenolic resin containing at least one aromatic moiety listed in Group 2 below. [ka]

[0068] The resin may have a weight average molecular weight of 500 to 20,000.

[0069] The resin may be contained in an amount of 0.1% by weight to 50% by weight based on the total content of the semiconductor photoresist composition.

[0070] When the resin is contained within the above content range, excellent etching resistance and heat resistance can be obtained.

[0071] On the other hand, the semiconductor photoresist composition preferably comprises the organometallic compound, polymer additive, solvent, and resin described above.

[0072] The semiconductor photoresist composition according to the above-described embodiment may further include additives, such as a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, or a combination thereof.

[0073] The surfactant may be, for example, but not limited to, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, or a combination thereof.

[0074] Examples of crosslinking agents include, but are not limited to, melamine-based crosslinking agents, substituted urea-based crosslinking agents, acrylic-based crosslinking agents, epoxy-based crosslinking agents, and polymer-based crosslinking agents. Examples of crosslinking agents having at least two crosslink-forming substituents that can be used include methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, acrylic methacrylate, 1,4-butanediol diglycidyl ether, glycidol, diglycidyl 1,2-cyclohexanedicarboxylate, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, and methoxymethylated thiourea.

[0075] The leveling agent is used to improve coating flatness during printing, and any known leveling agent that is commercially available can be used.

[0076] The organic acid may be, but is not limited to, p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, sulfonium fluoride salts, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or combinations thereof.

[0077] The quencher may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0078] The amount of these additives used can be easily adjusted depending on the desired physical properties, and they may also be omitted.

[0079] The semiconductor photoresist composition may further contain a silane coupling agent as an additive to enhance adhesion to a substrate (e.g., to improve the adhesive strength of the semiconductor photoresist composition to a substrate). Examples of the silane coupling agent include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; and silane compounds containing a carbon-carbon unsaturated bond, such as trimethoxy[3-(phenylamino)propyl]silane.

[0080] The semiconductor photoresist composition may not cause pattern collapse even when forming a pattern having a high aspect ratio. Therefore, the composition can be used in a photoresist process using light with a wavelength of 5 nm to 150 nm, for example, a photoresist process using light with a wavelength of 5 nm to 100 nm, for example, a photoresist process using light with a wavelength of 5 nm to 80 nm, for example, a photoresist process using light with a wavelength of 5 nm to 70 nm, for example, a photoresist process using light with a width of 5 nm to 50 nm, for example, a photoresist process using light with a wavelength of 5 nm to 40 nm, for example, a photoresist process using light with a wavelength of 5 nm to 30 nm, or for example, a photoresist process using light with a wavelength of 5 nm to 20 nm to form a fine pattern having a width of, for example, 5 nm to 100 nm, for example, a photoresist process using light with a wavelength of 5 nm to 100 nm, for example, a photoresist process using light with a wavelength of 5 nm to 80 nm, for example, a photoresist process using light with a wavelength of 5 nm to 50 nm, for example, a photoresist process using light with a wavelength of 5 nm to 30 nm, or for example, a photoresist process using light with a wavelength of 5 nm to 20 nm. Therefore, by using the semiconductor photoresist composition according to one embodiment, extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5 nm can be realized.

[0081] According to another embodiment, there is provided a method for forming a pattern using the semiconductor photoresist composition. For example, the formed pattern may be a photoresist pattern.

[0082] According to one embodiment, a method for forming a pattern includes forming a layer to be etched on a substrate; applying the semiconductor photoresist composition on the layer to be etched to form a photoresist layer; patterning the photoresist layer to form a photoresist pattern; and etching the layer to be etched using the photoresist pattern as an etching mask.

[0083] Hereinafter, a method for forming a pattern using the semiconductor photoresist composition will be described with reference to Fig. 1. Fig. 1 is a cross-sectional view illustrating a method for forming a pattern using the semiconductor photoresist composition according to the present invention.

[0084] Referring to FIG. 1(a), first, an etching target is prepared. An example of the etching target may be a thin film 102 formed on a semiconductor substrate 100. The following description will be limited to the case where the etching target is the thin film 102. The surface of the thin film 102 is cleaned to remove contaminants remaining on the thin film 102. The thin film 102 may be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film.

[0085] Next, a composition for forming a resist underlayer film to form a resist underlayer film 104 is coated on the surface of the cleaned thin film 102 by spin coating. However, this embodiment is not limited thereto, and various known coating methods, such as spray coating, dip coating, knife edge coating, and printing methods, such as inkjet printing and screen printing, may also be used.

[0086] The resist underlayer film coating step can be omitted, and the following description will be made of the case where the resist underlayer film is coated.

[0087] Thereafter, drying and baking steps are performed to form a resist underlayer film 104 on the thin film 102. The baking treatment can be performed at about 100 to about 500°C, for example, about 100 to about 300°C.

[0088] The resist underlayer film 104 is formed between the substrate 100 and the photoresist film 106, and can prevent non-uniformity of the photoresist linewidth and disruption of pattern formability when radiation reflected from the interface between the substrate 100 and the photoresist film 106 or from an interlayer hard mask is scattered into unintended photoresist regions.

[0089] 1(b), the semiconductor photoresist composition is coated on the resist underlayer film 104 to form a photoresist film 106. The photoresist film 106 may be formed by coating the semiconductor photoresist composition on a thin film 102 formed on a substrate 100 and then curing the composition through a heat treatment process.

[0090] More specifically, the step of forming a pattern using the semiconductor photoresist composition may include a step of applying the semiconductor photoresist composition onto the substrate 100 on which the thin film 102 has been formed by spin coating, slit coating, inkjet printing, etc., and a step of drying the applied semiconductor photoresist composition to form a photoresist film 106.

[0091] The semiconductor photoresist composition has already been explained in detail, so a duplicate explanation will be omitted.

[0092] 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.

[0093] Referring to FIG. 1(c), the photoresist film 106 is selectively exposed to light using a patterned mask 110.

[0094] For example, examples of light that can be used in the exposure process include light with short wavelengths such as activating radiation i-rays (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), as well as light with high energy wavelengths such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0095] More specifically, the exposure light in one embodiment may be short wavelength light having a wavelength range of 5 nm to 150 nm, or may be light having a high energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0096] The exposed region 106b of the photoresist film 106 has a different solubility from the unexposed region 106a of the photoresist film 106 by forming a polymer through a crosslinking reaction such as condensation between organometallic compounds.

[0097] Next, a second baking process is performed on the substrate 100. The second baking process can be performed at a temperature of about 90° C. to about 200° C. By performing the second baking process, the exposed region 106b of the photoresist film 106 becomes less soluble in a developer.

[0098] 1(d) shows a photoresist pattern 108 formed by dissolving and removing the photoresist film 106a corresponding to the unexposed region using a developer. Specifically, the photoresist film 106a corresponding to the unexposed region is dissolved and removed using an organic solvent such as 2-heptanone, thereby completing the photoresist pattern 108 corresponding to the negative tone image.

[0099] 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.

[0100] However, the photoresist pattern according to an embodiment is not necessarily limited to being formed as a negative tone image, and may also be formed as a positive tone image. In this case, developers that can be used to form a positive tone image include quaternary ammonium hydroxide compositions such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof.

[0101] As described above, the photoresist pattern 108 formed by exposure to light having a wavelength such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), or ArF excimer laser (wavelength 193 nm), as well as high-energy light such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-beam (electron beam), may have a thickness of 5 nm to 100 nm. For example, the photoresist pattern 108 may have a thickness of 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, or 5 nm to 20 nm.

[0102] Meanwhile, the photoresist pattern 108 may have a half-pitch of about 50 nm or less, e.g., 40 nm or less, e.g., 30 nm or less, e.g., 20 nm or less, e.g., 15 nm or less, and a pitch with a line width roughness of about 10 nm or less, about 5 nm or less, about 3 nm or less, or about 2 nm or less.

[0103] Next, the resist underlayer film 104 is etched using the photoresist pattern 108 as an etching mask, forming an organic layer pattern 112. The formed organic layer pattern 112 may also have a width corresponding to the photoresist pattern 108.

[0104] 1(e), the photoresist pattern 108 is used as an etching mask to etch the exposed thin film 102. As a result, the thin film is formed into a thin film pattern 114.

[0105] The thin film 102 can be etched by dry etching using an etching gas, such as CHF3, CF4, Cl2, BCl3, or a mixture thereof.

[0106] The thin film pattern 114 formed using the photoresist pattern 108 formed by the previous exposure process using an EUV light source may have a width corresponding to the photoresist pattern 108. For example, it may have a width of 5 nm to 100 nm, similar to the photoresist pattern 108. For example, the thin film pattern 114 formed by the exposure process using an EUV light source may have a width of 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, or 5 nm to 20 nm, similar to the photoresist pattern 108, and more specifically, may have a width of 20 nm or less. [Example]

[0107] The present invention will be described in more detail below with reference to examples of preparing the above-mentioned semiconductor photoresist composition, but the technical features of the present invention are not limited to these examples.

[0108] Synthesis of organometallic compounds Synthesis Example 1 340.7 g of t-butylSnPh and 300 g of propionic acid were placed in a 250 ml two-necked round-bottom flask and heated under reflux for 24 hours.

[0109] Unreacted propionic acid was removed under reduced pressure to obtain a compound represented by the following chemical formula 5. [ka]

[0110] Synthesis Example 2 30 ml of anhydrous pentane was added to 10 g of t-AmylSnCl, and the temperature was maintained at 0°C. Then, 7.4 g of diethylamine and 6.1 g of ethanol were added and stirred at room temperature for 1 hour. After the reaction was completed, the mixture was filtered, concentrated, and vacuum dried to obtain the compound represented by the following chemical formula 6. [ka]

[0111] Synthesis Example 3 10 g of dibutyltin dichloride was dissolved in 30 mL of ether, and then 70 mL of 1 M aqueous sodium hydroxide (NaOH) was added and stirred for 1 hour. After stirring, the resulting solid was filtered, washed three times with 25 mL of deionized water, and dried under reduced pressure at 100°C to obtain an organometallic compound with a weight-average molecular weight of 1,500, represented by the following chemical formula 7. [ka]

[0112] Synthesis Example 4: Synthesis of Compound 1a Under a nitrogen atmosphere, 20 g (59.86 mmol) of hexafluoro-2,3-bis(trifluoromethyl)-2,3-butanediol (perfluoropinacol), 7.79 g (59.86 mmol) of 2-(hydroxyethyl)methacrylate, and 18.84 g (71.84 mmol) of triphenylphosphine (PH3P) were mixed with 110 mL of diethyl ether and stirred. After stirring for 30 minutes, the mixture was cooled to 0°C and a mixture of 14.52 g (71.84 mmol) of diisopropyl azodicarboxylate (DIAD) and 35 mL of diethyl ether was slowly added dropwise over 2 hours. After stirring at room temperature (23°C) for 24 hours, the mixture was concentrated. The concentrated mixture was dissolved in dichloromethane and the synthesized product was isolated by column chromatography using silica gel. The mixture was again distilled under reduced pressure to synthesize 2-[3,3,3-Trifluoro-2-hydroxy-1,1,2-tris(trifluoromethyl)propoxy]ethyl 2-methyl-2-propenoate, represented by the following chemical formula 1a.

[0113] *1 H-NMR (Acetone-d6): δ1.90 (3H, t), 4.36 (4H, m), 5.63 (1H, t), 6.09 (1H, t), 8.34 (1H, s) *19 F-NMR (Acetone-d6): δ -70.12 (6F, m), -65.38 (6F, m) [ka]

[0114] Synthesis Example 5: Preparation of Polymer R1 A 250 mL two-neck round bottom flask was charged with the compound represented by Formula 1a (16.1 g, 36 mmol) and 110 g of diisoamyl ether (DIAE) under a nitrogen atmosphere and heated to an internal temperature of 85°C. Once the internal temperature reached 85°C, 14.7 g of a 25 wt% V-601 / DIAE solution (3.7 g, 16 mmol of V-601) was slowly added. After 6 hours, the reaction mixture was cooled to room temperature and concentrated to 50% solids. 270 g of heptane was added to the concentrated solution, and the resulting polymer was filtered. The filtered polymer was completely dissolved in 34 g of DIAE, and then precipitated twice by adding 270 g of heptane. The resulting solution was then completely dried to produce polymer R1 (Mw = 5,000). [ka]

[0115] Synthesis Example 6: Preparation of Polymer R2 Polymer R2 (Mw=5,500) was prepared in the same manner as in Synthesis Example 5, except that 8.83 g of a compound represented by the following Formula 1b (manufactured by HALOCARBON) was used instead of the compound represented by Formula 1a. [ka]

[0116] Synthesis Example 7: Preparation of Polymer R3 Polymer R3 (Mw=5,500) was prepared in the same manner as in Synthesis Example 5, except that 20 g of a compound represented by the following Formula 1c (manufactured by HALOCARBON) was used instead of the compound represented by Formula 1a. [ka]

[0117] Synthesis Example 8: Preparation of Polymer R4 Polymer R4 (Mw=5,300) was prepared in the same manner as in Synthesis Example 5, except that 20 g of a compound represented by the following Formula 1d (manufactured by HALOCARBON) was used instead of the compound represented by Formula 1a. [ka]

[0118] Synthesis Example 9: Preparation of Polymer R5 Polymer R5 (Mw=5,300) was prepared in the same manner as in Synthesis Example 5, except that 20 g of a compound represented by the following Formula 1e (manufactured by HALOCARBON) was used instead of the compound represented by Formula 1a. [ka]

[0119] (Production of semiconductor photoresist composition) Examples 1 to 15 and Comparative Examples 1 to 4 The organometallic compounds represented by Chemical Formulas 5 to 7 obtained in Synthesis Examples 1 to 3 and the polymers R1 to R5 obtained in Synthesis Examples 5 to 9 were dissolved in propylene glycol methyl ether acetate (PGMEA) 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 prepare semiconductor photoresist compositions according to Examples 1 to 15 and Comparative Examples 1 to 4.

[0120] [Table 1]

[0121] Evaluation 1: Evaluation of sensitivity and line edge roughness (LER) Each of the photoresist compositions according to the Examples and Comparative Examples was spin-coated at 1500 rpm for 30 seconds onto a 200 mm circular silicon wafer whose surface had been deposited with HMDS, baked at 110°C for 60 seconds (post-apply bake, PAB), and then left at room temperature (23±2°C) for 30 seconds.

[0122] Then, a linear array of 50 circular pads, each 500 μm in diameter, was projected onto the wafer coated with the photoresist composition using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). Pad exposure time was adjusted so that an increased EUV dose was applied to each pad.

[0123] The resist and substrate were then exposed and baked on a hot plate at 160°C for 120 seconds. The baked film was developed with PGMEA solvent to form a negative tone image. The process was terminated by a final hot plate bake at 150°C for 2 minutes.

[0124] 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 to measure sensitivity. LER was measured from the FE-SEM image, and then sensitivity and line edge roughness were evaluated according to the following criteria. The results are shown in Table 2.

[0125] [Sensitivity evaluation criteria] -A: 50mJ / cm 2 less than -B: 50mJ / cm 2 End [LER evaluation criteria] -○: 2nm or less -△: More than 2nm and less than 5nm -X: More than 5nm

[0126] Rating 2: Defect rating A lower SiON film, a spin-on carbon film, and an upper SiON film were formed in this order on a 12-inch silicon substrate. A 36 nm pitch 1:1 line / space photoresist pattern was formed on the upper SiON film by EUV lithography using the photoresist compositions according to the examples and comparative examples. The photoresist pattern was transferred to the lower SiON film by dry etching using plasma. All defects, including bridge defects between line patterns, were inspected in a bright field using a defect analyzer using a DUV laser. The inspected defects were classified using a SEM, and the number of detected defects per unit area (ea / cm) was calculated. 2 ) is expressed as

[0127] In this case, when the number of SLO defects when the photoresist supernatant liquid composition was not applied was converted to 100, the number of defects was marked as "○" when it was 80% or less, and the number of defects was marked as "X" when it was more than 80%.

[0128] [Table 2]

[0129] From the results in Table 2, it can be seen that the patterns formed using the semiconductor photoresist compositions according to Examples 1 to 15 exhibit superior sensitivity, LER, and resolution characteristics compared to those of Comparative Examples 1 to 4.

[0130] Although specific embodiments of the present invention have been described and illustrated above, it will be apparent to those skilled in the art that the present invention is not limited to the described embodiments and that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modifications and variations should not be understood individually from the technical spirit and perspective of the present invention, and the modified embodiments should be considered to fall within the scope of the claims of the present invention. [Explanation of symbols]

[0131] 100...substrate, 102...thin film, 104...resist underlayer film, 106...photoresist film, 106a...unexposed region, 106b...exposed region, 108...photoresist pattern, 112...organic film pattern, 110...patterned mask, 114...thin film pattern.

Claims

1. Organometallic compounds; A polymer additive comprising a structural unit represented by the following chemical formula 1; and A composition for semiconductor photoresist, comprising a solvent: 【Chemistry 1】 In the above Chemical Formula 1, R １ is hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, R ２ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, including a trifluoromethyl group and a hydroxy group, R ３ ~R ６ are each independently hydrogen, fluorine, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a combination thereof; n1 and n2 are each independently an integer from 0 to 10; n1+n2 is 1 or more, X １ is a single bond, -O-, -S-, -S(O)-, -S(O) ２ -, -C(O)-, -(CO)O-, -O(CO), -O(CO)O-, -NR ａ - (where R ａ is hydrogen, deuterium, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), or a combination thereof; * indicates a connection point.

2. The R ２ 2. The semiconductor photoresist composition according to claim 1, wherein is an alkyl group having 1 to 20 carbon atoms substituted with at least one trifluoromethyl group and at least one hydroxy group.

3. The R ２ 2. The semiconductor photoresist composition according to claim 1, wherein is an alkyl group having 1 to 10 carbon atoms substituted with two trifluoromethyl groups and one hydroxy group.

4. The composition for semiconductor photoresist according to claim 1, wherein the formula 1 is represented by the following formula 1-1: 【Chemistry 2】 In the above chemical formula 1-1, R １ is hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, R ３ ~R ６ are each independently hydrogen, fluorine, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a combination thereof; n1 and n2 are each independently an integer from 0 to 10; n1+n2 is 1 or more, X １ is a single bond, -O-, -S-, -S(O)-, -S(O) ２ -, -C(O)-, -(CO)O-, -O(CO), -O(CO)O-, -NR ａ - (where R ａ is hydrogen, deuterium, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), or a combination thereof; * indicates a connection point.

5. 2. The composition for semiconductor photoresist according to claim 1, wherein the structural unit represented by Chemical Formula 1 is one selected from the structural units listed in Group 1 below: 【Transformation 3】 In Group 1, R １ are each independently hydrogen or a methyl group; * indicates a connection point.

6. 2. The semiconductor photoresist composition of claim 1, wherein the polymer additive having the structural unit represented by Chemical Formula 1 is contained in an amount of 0.001 to 10 wt % based on 100 wt % of the semiconductor photoresist composition.

7. 2. The semiconductor photoresist composition of claim 1, wherein the polymer additive having the structural unit represented by Chemical Formula 1 is contained in an amount of 0.1 to 5 wt % based on 100 wt % of the semiconductor photoresist composition.

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

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

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

11. 2. The composition for semiconductor photoresist of claim 1, wherein the organometallic compound is represented by the following chemical formula 2: 【Chemistry 4】 In the above Chemical Formula 2, R ９ is selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms; R １０ ~R １２ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, an alkoxy group, and an aryloxy group (-OR ｂ , where R ｂ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), a carboxyl group (—O(CO)R ｃ , R ｃ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylamide or dialkylamide (—NR ｄ R ｅ , where R ｄ and R ｅ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), amidate (—NR ｆ (COR ｇ ), where R ｆ and R ｇ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), amidinato (—NR ｈ C (NR ｉ ) R ｊ , where R ｈ , R ｉ and R ｊ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylthio and arylthio (-SR ｋ , where R ｋ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), or a thiocarboxyl group (—S(CO)R ｌ , R ｌ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; R １０ ~R １２ At least one of alkoxy and aryloxy (—OR ｂ , where R ｂ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), a carboxyl group (—O(CO)R ｃ , R ｃ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylamide or dialkylamide (—NR ｄ R ｅ , where R ｄ and R ｅ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), amidate (—NR ｆ (COR ｇ ), where R ｆ and R ｇ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), amidinato (—NR ｈ C (NR ｉ ) R ｊ , where R ｈ , R ｉ and R ｊ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylthio and arylthio (-SR ｋ , where R ｋ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), and a thiocarboxyl group (—S(CO)R ｌ , R ｌ is selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof.

12. The R １０ ~R １２ At least one of alkoxy and aryloxy (—OR ｂ , where R ｂ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), and a carboxyl group (—O(CO)R ｃ , R ｃ is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof.

13. The R ９ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted aliphatic unsaturated organic group having 2 to 8 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 4 to 20 carbon atoms, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof; R ｂ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 8 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof; R ｃ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 8 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof.

14. 2. The composition for semiconductor photoresist of claim 1, wherein the organometallic compound is represented by the following Chemical Formula 3 or Chemical Formula 4: 【Transformation 5】 In the above Chemical Formula 3, R １３ is a hydrocarbyl group having 1 to 31 carbon atoms, where 0<z≦2 and 0<(z+x)≦4; 【Transformation 6】 In the above Chemical Formula 4, R １４ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated organic group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 4 to 30 carbon atoms, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof; X is sulfur (S), selenium (Se), or tellurium (Te); Y is -OR ｍ or -OC(=O)R ｎ and The R ｍ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; R ｎ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; The a, b, c, and d are each independently an integer of 1 to 20.

15. forming a film to be etched on a substrate; applying the semiconductor photoresist composition 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 etching the target layer using the photoresist pattern as an etching mask.

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