Semiconductor photoresist composition and method of forming pattern using the same

Abstract

Disclosed are a semiconductor photoresist composition and a method of forming a pattern using the same, the semiconductor photoresist composition comprising: a Sn-containing organometallic compound; a carboxylic acid compound represented by Chemical Formula 1; and a solvent.

Description

[0001] Cross - reference to related applications

[0002] This application claims the priority and benefit of Korean Patent Application No. 10 - 2024 - 0001133, filed with the Korean Intellectual Property Office on January 3, 2024, the entire content of which is incorporated herein by reference. Technical field

[0003] Embodiments of the present disclosure relate to a semiconductor photoresist composition and a method of forming a pattern using the composition. Background art

[0004] Extreme ultraviolet (EUV) lithography has received attention as a technology for manufacturing next - generation semiconductor devices. EUV lithography is a pattern - forming technology that uses EUV rays with a wavelength of 13.5 nanometers as an exposure light source. According to EUV lithography, extremely fine patterns (e.g., less than or equal to 20 nanometers) can be formed in the exposure process during semiconductor device manufacturing.

[0005] EUV lithography can be achieved by developing compatible photoresists capable of performing at a spatial resolution of less than or equal to 16 nanometers. Currently, efforts are being made to meet the insufficient specifications of traditional chemically amplified (CA) photoresists for next - generation devices, such as resolution, photosensitivity, and feature roughness (also referred to as line edge roughness or LER).

[0006] The inherent image blur caused by acid - catalyzed reactions in these polymer - type photoresists limits the resolution of small feature sizes, which has long existed in electron - beam (e - beam) lithography. Chemically amplified (CA) photoresists are designed to have high sensitivity, but due to their typical elemental composition reducing the light absorption rate of the photoresist at a wavelength of 13.5 nanometers, thereby reducing their sensitivity, CA photoresists may face more difficulties in part under EUV exposure.

[0007] Chemically amplified photoresists may encounter difficulties in small feature sizes due to roughness problems, and experiments show that due to the nature of the acid - catalyzed process, as the photosensitivity is partially reduced, the line edge roughness (LER) of chemically amplified photoresists increases. Therefore, due to these defects and problems of chemically amplified photoresists, a new type of high - performance photoresist would be beneficial to the semiconductor industry.

[0008] To overcome the disadvantages of the above-described chemically amplified (CA) organic photosensitive compositions, inorganic photosensitive compositions have been studied. Inorganic photosensitive compositions are mainly used for negative tone patterning with the ability to resist developer removal through chemical modification by a non-chemical amplification mechanism. Inorganic compositions contain inorganic elements with higher EUV absorption rates than hydrocarbon groups, and thus can ensure sensitivity through a non-chemical amplification mechanism. In addition, they are less sensitive to random effects, and thus have low line edge roughness and a relatively small number of defects.

[0009] Inorganic photoresists based on tungsten peroxypolyacids mixed with tungsten, niobium, titanium, and / or tantalum have been reported as radiation-sensitive materials for patterning.

[0010] These materials are effective for large pitch patterning in a bilayer configuration using far ultraviolet (deep UV), X-ray, and electron beam sources. Recently, impressive performance has been obtained when using a cationic hafnium metal oxide sulfate (HfSOx) material together with a peroxo complexing agent for imaging a 15-nanometer half-pitch (HP) by projection EUV exposure. The system exhibits the highest performance of non-chemically amplified photoresists and has a practical photosensitivity close to or suitable for EUV photoresist requirements. However, hafnium metal oxide sulfate materials with peroxo complexing agents have some practical disadvantages. First, these materials are coated in a corrosive sulfuric acid / hydrogen peroxide mixture and have insufficient shelf-life stability. Second, as a composite mixture, it is not easy to change its structure to improve performance. Third, development should be carried out in a 25 wt% tetramethylammonium hydroxide (TMAH) solution and / or the like with extremely high concentration.

[0011] Recently, active research has been conducted on tin-containing molecules, which have excellent extreme ultraviolet absorption properties. Among them, for organotin polymers, alkyl ligands dissociate through light absorption or the resulting secondary electrons and crosslink with adjacent chains through oxygen bonds, thereby achieving negative patterning that cannot be removed by organic developers. Such organotin polymers exhibit greatly improved sensitivity while maintaining resolution and line edge roughness, but for commercial availability, patterning characteristics still need to be further improved. SUMMARY OF THE INVENTION

[0012] Some embodiments of the present disclosure provide a semiconductor photoresist composition having excellent sensitivity and line edge roughness (LER) characteristics and improved resolution.

[0013] Some embodiments provide a method of forming a pattern using the semiconductor photoresist composition.

[0014] According to some embodiments, a semiconductor photoresist composition includes: a Sn-containing organometallic compound; a carboxylic acid compound represented by Chemical Formula 1; and a solvent.

[0015] [Chemical Formula 1]

[0016]

[0017] In Chemical Formula 1,

[0018] A is a substituted or unsubstituted C5 to C50 polycyclic aliphatic hydrocarbon group in which at least two rings are fused together, and

[0019] n is an integer greater than or equal to 1.

[0020] According to some embodiments, a method of forming a pattern includes forming an etch target film on a substrate, coating a semiconductor photoresist composition on the etch target film to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and etching the etch target film using the photoresist pattern as an etch mask.

[0021] According to some embodiments, the semiconductor photoresist composition can achieve excellent sensitivity, excellent line edge roughness, and excellent resolution. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The drawings, together with the specification, illustrate embodiments of the subject matter of the present disclosure and, together with the description, are used to explain the principles of the embodiments of the present disclosure.

[0023] Figures 1 - 5 is a cross-sectional view illustrating a method of forming a pattern using a semiconductor photoresist composition according to some embodiments.

[0024] REFERENCE NUMERAL DESCRIPTION

[0025] 100: Substrate;

[0026] 102: Thin film;

[0027] 104: Antireflective bottom layer;

[0028] 106: Photoresist layer;

[0029] 106a: Exposed area;

[0030] 106b: Unexposed area;

[0031] 108: Photoresist pattern;

[0032] 112: Organic film pattern;

[0033] 114: Thin film pattern. DETAILED DESCRIPTION

[0034] Hereinafter, embodiments will be described in more detail with reference to the accompanying drawings. In the following description of the subject matter of the present disclosure, well-known functions or structures will not be described in order to clarify the description of the embodiments of the present disclosure.

[0035] To clearly illustrate the embodiments of the present disclosure, certain descriptions and relationships may be omitted, and throughout the disclosure, the same or similar configuration elements are designated by the same reference numerals. In addition, since the dimensions and thicknesses of each configuration shown in the drawings may be arbitrarily shown for better understanding and ease of description, the present disclosure is not necessarily limited thereto.

[0036] In the drawings, the thicknesses of layers, films, panels, regions, etc. may be exaggerated for clarity. In the drawings, the thicknesses of some layers or regions, etc. may be exaggerated for clarity. It should be understood that if an element such as a layer, film, region, or substrate is referred to as "on" another element, it may be directly on the other element or there may also be intervening elements.

[0037] As used herein, "substituted" means that a hydrogen atom is replaced by deuterium, a halogen, a hydroxyl group, a mercapto 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 cycloaliphatic 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 cycloaliphatic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), a C1 to C30 alkyl group, a C1 to C10 haloalkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a C1 to C20 sulfide group, or a combination thereof. "Unsubstituted" means that the hydrogen atom is not replaced by another substituent and the hydrogen atom remains.

[0038] As used herein, if no other definition is provided, "alkyl" refers to a straight-chain or branched-chain aliphatic hydrocarbon group. The alkyl group can be a "saturated alkyl group" that does not contain any double or triple bonds.

[0039] The alkyl group can be a C1 to C8 alkyl group. For example, the alkyl group can 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 can be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or 2,2-dimethylpropyl.

[0040] As used herein, if no other definition is provided, "cycloalkyl" refers to a monovalent cyclic aliphatic hydrocarbon group.

[0041] The cycloalkyl group can be a C3 to C8 cycloalkyl group, for example, a C3 to C7 cycloalkyl group, a C3 to C6 cycloalkyl group, a C3 to C5 cycloalkyl group, or a C3 to C4 cycloalkyl group. For example, the cycloalkyl group can be cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl, but is not limited thereto.

[0042] As used herein, "aliphatic unsaturated organic group" refers to a hydrocarbon group including a double bond, a triple bond, or a combination thereof between carbon atoms in the molecule.

[0043] The aliphatic unsaturated organic group can be a C2 to C8 aliphatic unsaturated organic group. For example, the aliphatic unsaturated organic group can be a C2 to C7 aliphatic unsaturated organic group, a C2 to C6 aliphatic unsaturated organic group, a C2 to C5 aliphatic unsaturated organic group, or a C2 to C4 aliphatic unsaturated organic group. For example, the C2 to C4 aliphatic unsaturated organic group can be vinyl, ethynyl, allyl, 1-propenyl, 1-methyl-1-propenyl, 2-propenyl, 2-methyl-2-propenyl, 1-propynyl, 1-methyl-1-propynyl, 2-propynyl, 2-methyl-2-propynyl, 1-buteneyl, 2-buteneyl, 3-buteneyl, 1-butynyl, 2-butynyl, or 3-butynyl.

[0044] As used herein, "aryl" refers to a substituent in which all atoms in the cyclic substituent have p orbitals and these p orbitals are conjugated, and can include a monocyclic functional group, a polycyclic functional group, or a fused ring (for example, a ring sharing adjacent carbon atom pairs) functional group.

[0045] As used herein, "heteroaryl" refers to an aryl including at least one heteroatom selected from N, O, S, P, and Si. Two or more heteroaryls are directly connected by a σ bond, or if the heteroaryl includes two or more rings, these two or more rings can be fused together. If the heteroaryl is a fused ring, each ring can include one to three heteroatoms.

[0046] As used herein, unless otherwise defined, "alkenyl" refers to an aliphatic unsaturated alkenyl group including at least one double bond as a straight-chain or branched-chain aliphatic hydrocarbon group.

[0047] As used herein, unless otherwise defined, "alkynyl" refers to an aliphatic unsaturated alkynyl group including at least one triple bond as a straight-chain or branched-chain aliphatic hydrocarbon group.

[0048] Hereinafter, a semiconductor photoresist composition according to some embodiments will be described.

[0049] The semiconductor photoresist composition according to some embodiments includes a Sn-containing organometallic compound, a carboxylic acid compound represented by Chemical Formula 1, and a solvent.

[0050] [Chemical Formula 1]

[0051]

[0052] In Chemical Formula 1,

[0053] A is a substituted or unsubstituted C5 to C50 polycyclic aliphatic hydrocarbon group in which at least two rings are fused together, and

[0054] n is an integer greater than or equal to 1.

[0055] The semiconductor photoresist composition includes a carboxylic acid compound represented by Chemical Formula 1 (for example, a carboxylic acid compound including a polycyclic aliphatic hydrocarbon group), thereby improving sensitivity and line edge roughness and achieving excellent resolution.

[0056] In the present disclosure, "polycyclic aliphatic hydrocarbon group" refers to a fused ring structure in which two or more rings share one or more carbon atom pairs. For example, it may mean a bridged polycyclic aliphatic hydrocarbon group having 5 to 50 carbon atoms.

[0057] The polycyclic aliphatic hydrocarbon group may include, for example, adamantane, norbornane, isonorbornane, tricyclodecane, and / or tetracyclododecane, but is not limited thereto.

[0058] A may be a substituted or unsubstituted adamantyl group, a substituted or unsubstituted norbornyl group, a substituted or unsubstituted isonorbornyl group, a substituted or unsubstituted tricyclodecanyl group, a substituted or unsubstituted tetracyclododecanyl group, or a combination thereof.

[0059] As an example, the carboxylic acid compound represented by Chemical Formula 1 may be one of the compounds listed in Group 1.

[0060] [Group 1]

[0061]

[0062] Based on 100% by weight of the semiconductor photoresist composition, the carboxylic acid compound represented by Chemical Formula 1 may be included in an amount of about 0.01 to about 10 wt%.

[0063] For example, based on 100% by weight of the semiconductor photoresist composition, the carboxylic acid compound represented by Chemical Formula 1 may be included in an amount of about 0.01 to about 5 wt% or about 0.05 to about 3 wt%.

[0064] Based on 100% by weight of the semiconductor photoresist composition, the Sn-containing organometallic compound may be included in an amount of about 0.5 wt% to about 30 wt%.

[0065] According to some embodiments, a semiconductor photoresist composition can improve the sensitivity of the photoresist by including an organometallic compound containing Sn and a carboxylic acid compound represented by Chemical Formula 1 within the above content ranges.

[0066] According to some embodiments, a semiconductor photoresist composition can include an organometallic compound containing Sn and a carboxylic acid compound represented by Chemical Formula 1 in a weight ratio of about 99:1 to about 80:20. For example, a semiconductor photoresist composition can include an organometallic compound containing Sn and a carboxylic acid compound represented by Chemical Formula 1 in a weight ratio of about 95:5 to about 85:15.

[0067] If the weight ratio of the organometallic compound containing Sn and the carboxylic acid compound represented by Chemical Formula 1 satisfies the above range, a semiconductor photoresist composition with excellent sensitivity can be provided.

[0068] The organometallic compound containing Sn can include at least one selected from an organic oxy group and an organic carbonyl oxy group.

[0069] The organometallic compound can be represented by Chemical Formula 2.

[0070] [Chemical Formula 2]

[0071]

[0072] In Chemical Formula 2,

[0073] R 2 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 aralkyl group.

[0074] R 3 to R 5 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 aralkyl group, an alkoxy group and / or an aryloxy group (-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 , where Rc is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an alkylamide or a dialkylamide (-NR d R e , wherein R d and R e are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an amido group (-NR f (COR g ), wherein R f and R g are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an amidino group (-NR h C(NR i )R j , wherein R h , R i and R j are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an alkylthio group and / or an arylthio group (-SR k , wherein R k is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), or a thiocarboxy group (-S(CO)R l , wherein R l is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), and

[0075] R 3 to R5 at least one selected from 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), carboxyl (-O(CO)R c , where R c is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), alkylamide and / or dialkylamide (-NR d R e , where R d and R e are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), amido (-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), amidino (-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 kis a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof) and a thiocarboxy group (-S(CO)R l , where R l is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof).

[0076] In some embodiments, at least one of R 3 to R 5 can be selected from an alkoxy group and an aryloxy group (-OR b , where R b is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), and a carboxy group (-O(C=O)R c , where R c is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof).

[0077] In an embodiment, the compound represented by Formula 2 includes -OR b or -OC(=O)R c as a ligand, such that a pattern formed using a semiconductor photoresist composition containing the same can exhibit excellent ultimate resolution.

[0078] In an embodiment, -OR b or -OC(=O)R c ligands can determine the solubility of the compound represented by Formula 2 in a solvent.

[0079] R 2 can be a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C4-C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof,

[0080] R b may be a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof, and

[0081] R c may be hydrogen, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

[0082] R 2 may be methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, formyl, acetyl, propionyl, butyryl, valeryl, ethoxy, propoxy, or a combination thereof,

[0083] R b may be ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or a combination thereof, and

[0084] R c may be hydrogen, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or a combination thereof.

[0085] In addition, the Sn-containing organometallic compound may be represented by Chemical Formula 3 or Chemical Formula 4.

[0086] [Chemical Formula 3]

[0087] R 6 z SnO (2-(z / 2)-(x / 2)) (OH) x

[0088] In Chemical Formula 3,

[0089] R 6 is a C1-C31 hydrocarbon group (e.g., a C1-C31 hydrocarbon group), where 0 < z ≤ 2 and 0 < (z + x) ≤ 4;

[0090] [Chemical Formula 4]

[0091] R 7 n1 Sn m1 X l1 Y k1

[0092] Wherein, in Chemical Formula 4,

[0093] R 7 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C4-C30 heteroaryl group, a carbonyl group, an oxiranyl group, an oxetanyl group, or a combination thereof,

[0094] X is sulfur (S), selenium (Se), or tellurium (Te),

[0095] Y is -OR m or -OC(=O)R n ,

[0096] wherein R m is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof, and,

[0097] R n is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof, and

[0098] n1, m1, l1, and k1 are each independently an integer in the range of 1 to 20.

[0099] The solvent of the semiconductor photoresist composition according to some embodiments may be an organic solvent, and for example, it may be an aromatic compound (e.g., xylene, toluene, etc.), an alcohol (e.g., 4-methyl-2-pentenol, 4-methyl-2-propanol, 1-butanol, methanol, isopropanol, 1-propanol, etc.), an ether (e.g., anisole, tetrahydrofuran, etc.), an ester (n-butyrate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, etc.), a ketone (e.g., methyl ethyl ketone, 2-heptanone, etc.), or a mixture thereof, but not limited thereto.

[0100] In addition to the Sn-containing organometallic compound, carboxylic acid compound represented by Chemical Formula 1, and solvent mentioned above, the semiconductor photoresist composition according to some embodiments may further include a resin.

[0101] The resin may be a phenolic resin containing at least one Group 2 aromatic moiety.

[0102] [Group 2]

[0103]

[0104] The resin may have a weight-average molecular weight of about 500 to about 20,000.

[0105] Based on the total amount of the semiconductor photoresist composition, the resin may be included in an amount of about 0.1 wt% to about 50 wt%.

[0106] If the resin is included in the above content range, it may have excellent etching resistance and heat resistance.

[0107] The semiconductor photoresist composition according to some embodiments may consist of the Sn-containing organometallic compound, carboxylic acid compound represented by Chemical Formula 1, solvent, and resin mentioned above.

[0108] The semiconductor photoresist composition according to an embodiment may further include additives as needed or desired. Examples of the additives may be a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, or a combination thereof.

[0109] The surfactant may include, for example, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, or a combination thereof, but is not limited thereto.

[0110] The crosslinking agent may be, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, an acrylic-based crosslinking agent, an epoxy-based crosslinking agent, and / or a polymer-based crosslinking agent, but is not limited thereto. It may be a crosslinking agent having at least two substituents for forming crosslinks. For example, compounds such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, methyl methacrylate, 1,4-butanediol diglycidyl ether, glycidol, diglycidyl 1,2-cyclohexanedicarboxylate, trimethylolpropane triglycidyl ether, 1,3-bis(glycidyloxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, and / or methoxymethylated thiourea, and / or the like.

[0111] The leveling agent may be used to improve the coating flatness during the printing process and may be any suitable leveling agent commonly used in the art.

[0112] The organic acid may include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, fluorosulfonate, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or a combination thereof, but is not limited thereto.

[0113] The quencher may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0114] In some embodiments, the semiconductor photoresist composition according to the present disclosure may be mixed with an acidic compound different from the carboxylic acid compound represented by Chemical Formula 1 described above. Examples of the acidic compound that can be mixed include organic acids, sulfonic acids, phosphonic acids, etc.

[0115] The usage amount of the additive can be controlled according to suitable or desired properties.

[0116] In an embodiment, the semiconductor photoresist composition may further include a silane coupling agent as an adhesion enhancer to improve the close contact force with the substrate (for example, to improve the adhesion of the semiconductor photoresist composition to the substrate). The silane coupling agent may be, for example, a silane compound including a carbon-carbon unsaturated bond, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; and / or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; trimethoxy[3-(phenylamino)propyl]silane, and / or the like, but is not limited thereto.

[0117] The semiconductor photoresist composition can form a pattern with a high aspect ratio without collapsing. Thus, in order to form a fine pattern having a width of, for example, about 5 nanometers to about 100 nanometers, such as about 5 nanometers to about 80 nanometers, such as about 5 nanometers to about 70 nanometers, such as about 5 nanometers to about 50 nanometers, such as about 5 nanometers to about 40 nanometers, such as about 5 nanometers to about 30 nanometers, or such as about 5 nanometers to about 20 nanometers, the semiconductor photoresist composition can be used in a lithography process using light in a wavelength range from about 5 nanometers to about 150 nanometers, such as about 5 nanometers to about 100 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 50 nanometers, about 5 nanometers to about 30 nanometers, or about 5 nanometers to about 20 nanometers. Thus, the semiconductor photoresist composition according to some embodiments can be used to achieve extreme ultraviolet lithography using an EUV light source that provides light with a wavelength of about 13.5 nanometers.

[0118] According to some embodiments, a method of forming a pattern using the foregoing semiconductor photoresist composition is provided. For example, the fabricated pattern may be a photoresist pattern.

[0119] The method of forming a pattern according to some embodiments includes forming an etching target film on a substrate, coating a semiconductor photoresist composition on the etching target film to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and etching the etching target film using the photoresist pattern as an etching mask.

[0120] Hereinafter, with reference to Figures 1 - 5 a method of forming a pattern using a semiconductor photoresist composition according to an embodiment is described. Figures 1 - 5 is a cross-sectional view showing a method of forming a pattern using a semiconductor photoresist composition according to some embodiments.

[0121] With reference to Figure 1 , an object for etching is prepared. The object for etching may be a thin film 102 formed on a semiconductor substrate 100. Hereinafter, the object for etching is defined as the thin film 102. The surface of the thin film 102 is cleaned to remove impurities and / or the like remaining thereon. The thin film 102 may be, for example, a silicon nitride layer, a polysilicon layer, and / or a silicon oxide layer.

[0122] Subsequently, a resist underlayer composition for forming a resist underlayer 104 is spin-coated on the surface of the cleaned thin film 102. However, the embodiments are not limited thereto, and various suitable coating methods may be used, such as spraying, dip coating, knife-edge coating, printing methods (such as inkjet printing and / or screen printing), and / or similar methods.

[0123] The coating process of the resist underlayer may be omitted. Hereinafter, a process including coating the resist underlayer is further described.

[0124] Then, the coated composition is dried and baked to form a resist underlayer 104 on the thin film 102. The baking may be performed at a temperature of about 100°C to about 500°C (for example, about 100°C to about 300°C).

[0125] The resist underlayer 104 is formed between the substrate 100 and the photoresist layer 106, and thus it is possible to prevent or reduce the non-uniformity of the photoresist line width and the reduction of the pattern forming ability that may occur due to light scattering from the interface between the substrate 100 and the photoresist layer 106 and / or the hard mask between the layers to an unintended photoresist region.

[0126] With reference to Figure 2, a photoresist layer 106 is formed by coating a semiconductor photoresist composition on the underlying resist layer 104. The photoresist layer 106 is obtained by coating the above-mentioned semiconductor photoresist composition on the thin film 102 formed on the substrate 100 and then curing it by heat treatment.

[0127] In an embodiment, forming a pattern using a semiconductor photoresist composition may include coating the semiconductor photoresist composition on the substrate 100 having the thin film 102 by spin coating, slot coating, inkjet printing, and / or similar methods, and then drying it to form the photoresist layer 106.

[0128] The semiconductor photoresist composition has been described in detail and will not be elaborated here.

[0129] Subsequently, the substrate 100 having the photoresist layer 106 is subjected to a first baking process. The first baking process can be performed at a temperature of about 80°C to about 120°C.

[0130] Refer to Figure 3 , the photoresist layer 106 can be selectively exposed using a patterning mask 110.

[0131] For example, the exposure can use actinic radiation including light having a high energy wavelength (such as EUV (extreme ultraviolet; wavelength of about 13.5 nm), electron beam (E-Beam), and / or similar light) and a short wavelength (such as i-line (wavelength of about 365 nm), KrF excimer laser (wavelength of about 248 nm), ArF excimer laser (wavelength of about 193 nm), and / or similar light).

[0132] According to some embodiments, the light used for exposure can have a short wavelength and a high energy wavelength in the range of about 5 nm to about 150 nm, for example, EUV (extreme ultraviolet; wavelength 13.5 nm), electron beam (E-Beam), and / or similar light.

[0133] The exposed area 106a of the photoresist layer 106 and the unexposed area 106b of the photoresist layer 106 have different solubilities, which is achieved by forming a polymer formed by a crosslinking reaction (such as a condensation reaction) between organometallic compounds.

[0134] Subsequently, the substrate 100 is subjected to a second baking process. The second baking process can be performed at a temperature of about 90°C to about 200°C. Due to the second baking process, the exposed area 106a of the photoresist layer 106 becomes insoluble in the developer.

[0135] In Figure 4Therein, a developer is used to dissolve and remove the non-exposed region 106b of the photoresist layer to form a photoresist pattern 108. For example, by using an organic solvent (such as 2-heptanone and / or the like) to dissolve and remove the non-exposed region 106b of the photoresist layer, the photoresist pattern 108 corresponding to a negative image is completed.

[0136] As described above, according to some embodiments, the developer used in the method of forming a pattern can be an organic solvent. According to some embodiments, the organic solvent used in the method of forming a pattern can be, for example, ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone and / or the like, alcohols such as 4-methyl-2-pentanol, 1-butanol, isopropyl alcohol, 1-propanol, methanol and / or the like, esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone and / or the like, aromatic compounds such as benzene, xylene, toluene and / or the like, or a combination thereof.

[0137] However, the photoresist pattern according to some embodiments is not necessarily limited to a negative image, but can be formed to have a positive tone image. Herein, the developer used to form a positive image can be a quaternary ammonium hydroxide composition such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or a combination thereof.

[0138] As described above, exposure to light having high energy such as extreme ultraviolet light (EUV; wavelength 13.5 nanometers), electron beam (E-Beam) and / or the like, and light having a wavelength such as i-line (wavelength of about 365 nanometers), KrF excimer laser (wavelength of about 248 nanometers), ArF excimer laser (wavelength of about 193 nanometers) and / or the like can provide a photoresist pattern 108 having a thickness width of about 5 nanometers to about 100 nanometers. For example, the photoresist pattern 108 can have a thickness width of about 5 nanometers to about 90 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 70 nanometers, about 5 nanometers to about 60 nanometers, about 5 nanometers to about 50 nanometers, about 5 nanometers to about 40 nanometers, about 5 nanometers to about 30 nanometers or about 5 nanometers to about 20 nanometers.

[0139] In an embodiment, the photoresist pattern 108 can have a pitch with a half pitch less than or equal to about 50 nanometers, such as less than or equal to about 40 nanometers, such as less than or equal to about 30 nanometers, such as less than or equal to about 20 nanometers, such as less than or equal to about 15 nanometers, and a line width roughness less than or equal to about 10 nanometers, less than or equal to about 5 nanometers, less than or equal to about 3 nanometers or less than or equal to about 2 nanometers.

[0140] Subsequently, the underlying resist 104 is etched using the photoresist pattern 108 as an etch mask. Through this etching process, an organic film pattern 112 is formed. The organic film pattern 112 may also have a width corresponding to that of the photoresist pattern 108.

[0141] Refer to Figure 5 , and the exposed thin film 102 is etched by applying the photoresist pattern 108 as an etch mask. As a result, the thin film is formed into a thin film pattern 114.

[0142] The etching of the thin film 102 can be, for example, dry etching using an etch gas, and the etch gas can be, for example, CHF3, CF4, Cl2, BCl3, and / or a mixed gas thereof.

[0143] In the exposure process, the thin film pattern 114 formed using the photoresist pattern 108 formed by an exposure process performed using an EUV light source may have a width corresponding to that of the photoresist pattern 108. For example, the thin film pattern 114 may have a width of 5 nanometers to 100 nanometers equal to that of the photoresist pattern 108. For example, the thin film pattern 114 formed using the photoresist pattern 108 formed by an exposure process performed using an EUV light source may have a width of about 5 nanometers to about 90 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 70 nanometers, about 5 nanometers to about 60 nanometers, about 5 nanometers to about 50 nanometers, about 5 nanometers to about 40 nanometers, about 5 nanometers to about 30 nanometers, or about 5 nanometers to about 20 nanometers, and for example, a width less than or equal to about 20 nanometers, the same as the width of the photoresist pattern 108.

[0144] After that, embodiments of the present disclosure will be described in more detail by the following preparation examples of the semiconductor photoresist composition. However, the present disclosure is not technically limited by the following examples.

[0145] Synthesis of Organometallic Compounds

[0146] Synthesis Example 1

[0147] In a 250 - milliliter two - necked round - bottom flask, 40.7 grams of t - butyltin triphenyl (t - butylSnPh3) and 300 grams of propionic acid were added, and then heated under reflux conditions for 24 hours.

[0148] The unreacted propionic acid was removed under reduced pressure to obtain the compound represented by Chemical Formula 5.

[0149] [Chemical Formula 5]

[0150]

[0151] Synthesis Example 2

[0152] 30 mL of anhydrous pentane was added to 10 g of t-AmylSnCl3, and then it was kept at 0 °C. 7.4 g of diethylamine and 6.1 g of ethanol were added thereto, and then it was stirred at room temperature for 1 hour. After the reaction was completed, the resulting product was filtered, concentrated, and dried under vacuum to obtain the compound represented by Chemical Formula 6.

[0153] [Chemical Formula 6]

[0154]

[0155] Synthesis Example 3

[0156] 10 g of dibutyltin dichloride was dissolved in 30 mL of diethyl ether. 70 mL of 1 mol / L aqueous sodium hydroxide (NaOH) solution was added thereto, and then it was stirred for 1 hour. After stirring, the solid produced therein was filtered, washed three times with 25 mL of deionized water, and dried under reduced pressure at 100 °C to obtain the organometallic compound represented by Chemical Formula 7, with a weight average molecular weight of 1,500.

[0157] [Chemical Formula 7]

[0158]

[0159] Preparation of Semiconductor Photoresist Composition

[0160] Examples 1 to 12, and Comparative Examples 1 to 9

[0161] The compounds represented by Chemical Formulas 5 to 7 according to Synthesis Examples 1 to 3 and the carboxylic acid compound represented by Chemical Formula 1 were dissolved in propylene glycol methyl ether acetate (PGMEA) at the respective weight ratios shown in Table 1, and then filtered through a 0.1-μm polytetrafluoroethylene (PTFE) syringe filter to prepare each semiconductor photoresist composition.

[0162] Table 1

[0163]

[0164] Evaluation 1: Evaluation of Sensitivity and Line Edge Roughness (LER)

[0165] Each of the semiconductor photoresist compositions according to the examples and comparative examples was spin-coated on a 200-mm circular silicon substrate having hexamethyldisilazane (HMDS) deposited on its surface at 1500 rpm for 30 seconds, baked at 110 °C (post-application bake (PAB)) for 60 seconds, and allowed to stand at room temperature (23 ± 2 °C) for 30 seconds.

[0166] Subsequently, on a substrate coated with a photoresist composition, a line array consisting of 50 circular pads, each with a diameter of 500 micrometers, was projected using extreme ultraviolet light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). Here, the exposure time of the pads was adjusted to apply an increased extreme ultraviolet dose to each pad.

[0167] Subsequently, the resist and the substrate were exposed on a hot plate at 160 °C for 120 seconds and then baked. The baked film was developed with a propylene glycol monomethyl ether acetate solvent to form a negative image. Finally, it was baked on a hot plate at 150 °C for 2 minutes to complete the process.

[0168] The remaining resist thickness of the exposed pads was measured using an ellipsometer. After measuring the remaining thickness for each exposure dose and plotting it as a function of the exposure dose, and measuring the line edge roughness (LER) from the FE-SEM images, the sensitivity and the line edge roughness were evaluated according to the following criteria, and the results are shown in Table 2.

[0169] Sensitivity evaluation criteria

[0170] -A: Less than 16 mJ / cm²

[0171] -B: Greater than or equal to 16 mJ / cm²

[0172] LER evaluation criteria

[0173] -○: Less than or equal to 2 nm

[0174] -△: Greater than 2 nm and less than or equal to 5 nm

[0175] -X: Greater than 5 nm

[0176] Evaluation 2: Evaluation of resolution (CD)

[0177] After completing the process, a line / space CD pattern was formed on the patterned wafer, and then it was transferred to a critical dimension scanning electron microscope (CD-SEM) measurement device (GC-9380, Hitachi) to measure the CD (critical dimension) size of the region with a half pitch of 14 nm of the mask pattern, and the minimum value in the space CD (i.e., the distance between the lines) is shown in Table 2.

[0178] Table 2

[0179]

[0180] Referring to the results in Table 2, it can be seen that the patterns formed using the semiconductor photoresist compositions of Examples 1 to 12 respectively exhibit excellent sensitivity, line edge roughness, and resolution characteristics compared to the patterns formed using the semiconductor photoresist compositions of Comparative Examples 1 to 9 respectively.

[0181] In the foregoing, certain embodiments have been described and illustrated. However, it should be apparent to those of ordinary skill in the art that the present disclosure is not limited to the described embodiments, and various modifications and conversions can be made without departing from the spirit and scope of the present disclosure. Therefore, these modified or converted embodiments should not be understood separately from the technical idea and aspects of the present disclosure, and the modified embodiments are within the scope of the claims of the present disclosure and their equivalents.

Claims

1. A semiconductor photoresist composition, comprising: a Sn-containing organometallic compound; a carboxylic acid compound represented by Chemical Formula 1; and a solvent: [Chemical Formula 1] Wherein, in Chemical Formula 1, A is a substituted or unsubstituted C5 to C50 polycyclic aliphatic hydrocarbon group in which at least two rings are fused together, and n is an integer greater than or equal to 1.

2. The semiconductor photoresist composition according to claim 1, wherein: A is a substituted or unsubstituted adamantyl group, a substituted or unsubstituted norbornyl group, a substituted or unsubstituted isonorbornyl group, a substituted or unsubstituted tricyclodecanyl group, a substituted or unsubstituted tetracyclododecanyl group, or a combination thereof.

3. The semiconductor photoresist composition according to claim 1, wherein: the carboxylic acid compound represented by Chemical Formula 1 is one selected from the compounds listed in Group 1: [Group 1] 4. The semiconductor photoresist composition according to claim 1, wherein: based on 100% by weight of the semiconductor photoresist composition, the carboxylic acid compound represented by Chemical Formula 1 is included in an amount of 0.01% to 10% by weight.

5. The semiconductor photoresist composition according to claim 1, wherein: based on 100% by weight of the semiconductor photoresist composition, the carboxylic acid compound represented by Chemical Formula 1 is included in an amount of 0.05% to 3% by weight.

6. The semiconductor photoresist composition according to claim 1, wherein: based on 100% by weight of the semiconductor photoresist composition, the Sn-containing organometallic compound is included in an amount of 0.5% to 30% by weight.

7. The semiconductor photoresist composition according to claim 1, wherein: the weight ratio of the included Sn-containing organometallic compound and the carboxylic acid compound represented by Chemical Formula 1 is 99:1 to 80:

20.

8. The semiconductor photoresist composition according to claim 1, wherein: the semiconductor photoresist composition further includes additives such as a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quenching agent, or a combination thereof.

9. The semiconductor photoresist composition according to claim 1, wherein: the Sn-containing organometallic compound includes at least one selected from the groups of organic oxy and organic carbonyl oxy.

10. The semiconductor photoresist composition according to claim 1, wherein: the Sn-containing organometallic compound is represented by Chemical Formula 2: [Chemical Formula 2] Wherein, in Chemical Formula 2, R 2 selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C6-C30 aralkyl, R 3 to R 5 each independently is a substituted or unsubstituted C1 - C20 alkyl group; a substituted or unsubstituted C3 - C20 cycloalkyl group; a substituted or unsubstituted C2 - C20 alkenyl group; a substituted or unsubstituted C2 - C20 alkynyl group; a substituted or unsubstituted C6 - C30 aryl group; a substituted or unsubstituted C6 - C30 aralkyl group; an alkoxy group and / or an aryloxy group (-OR b ), where R b is a substituted or unsubstituted C1 - C20 alkyl group, a substituted or unsubstituted C3 - C20 cycloalkyl group, a substituted or unsubstituted C2 - C20 alkenyl group, a substituted or unsubstituted C2 - C20 alkynyl group, a substituted or unsubstituted C6 - C30 aryl group, or a combination thereof; a carboxyl group (-O(CO)R c ), where R c is hydrogen, a substituted or unsubstituted C1 - C20 alkyl group, a substituted or unsubstituted C3 - C20 cycloalkyl group, a substituted or unsubstituted C2 - C20 alkenyl group, a substituted or unsubstituted C2 - C20 alkynyl group, a substituted or unsubstituted C6 - C30 aryl group, or a combination thereof; an alkylamide or a dialkylamide (-NR d R e ), where R d and R e each independently is hydrogen, a substituted or unsubstituted C1 - C20 alkyl group, a substituted or unsubstituted C3 - C20 cycloalkyl group, a substituted or unsubstituted C2 - C20 alkenyl group, a substituted or unsubstituted C2 - C20 alkynyl group, a substituted or unsubstituted C6 - C30 aryl group, or a combination thereof; an amide group (-NR f (COR g ))), where R f and R g each independently is hydrogen, a substituted or unsubstituted C1 - C20 alkyl group, a substituted or unsubstituted C3 - C20 cycloalkyl group, a substituted or unsubstituted C2 - C20 alkenyl group, a substituted or unsubstituted C2 - C20 alkynyl group, a substituted or unsubstituted C6 - C30 aryl group, or a combination thereof; an amidino group (-NR h C(NR i )R j ), where R h , R i and R j each independently is hydrogen, a substituted or unsubstituted C1 - C20 alkyl group, a substituted or unsubstituted C3 - C20 cycloalkyl group, a substituted or unsubstituted C2 - C20 alkenyl group, a substituted or unsubstituted C2 - C20 alkynyl group, a substituted or unsubstituted C6 - C30 aryl group, or a combination thereof; an alkylthio group and / or an arylthio group (-SR k ), wherein R k is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof; or a thiocarboxyl group (-S(CO)R l ), wherein R l is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof, and R 3 to R 5 at least one selected from 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); carboxyl (-O(C=O)R c ), where R c is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; alkylamide or dialkylamide (-NR d R e ), where R d and R e are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; amido (-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; amidino (-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-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof; and a thiocarboxyl group (-S(CO)R l ), where R l is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof.

11. The semiconductor photoresist composition according to claim 10, wherein: R 3 to R 5 at least one selected from 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; and carboxy (-O(C=O)R c ), where 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.

12. The semiconductor photoresist composition according to claim 10, wherein: R 2 is a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C4-C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof, R b is a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof, and R c is hydrogen, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

13. The semiconductor photoresist composition according to claim 1, wherein: the Sn-containing organometallic compound is represented by Chemical Formula 3 or Chemical Formula 4: [Chemical Formula 3] R 6 z SnO (2-(z / 2)-(x / 2)) (OH) x Wherein, in Chemical Formula 3, R 6 is a C1 to C31 hydrocarbyl group, where 0 < z ≤ 2 and 0 < (z + x) ≤ 4; [Chemical Formula 4] R 7 n1 Sn m1 X l1 Y k1 Wherein, in Chemical Formula 4, R 7 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C4-C30 heteroaryl group, a carbonyl group, an oxiranyl group, an oxetanyl group, or a combination thereof. X is sulfur, selenium or tellurium, Y is -OR m or -OC(=O)R n , wherein R m is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof, and R n is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof, and n1, m1, l1 and k1 are each independently an integer in the range of 1 to 20.

14. A method of forming a pattern, comprising: providing an etching target film on a substrate; Coat the semiconductor photoresist composition according to any one of claims 1 to 13 on the etching target film to form a photoresist layer; Pattern the photoresist layer to form a photoresist pattern; And Use the photoresist pattern as an etching mask to etch the etching target film.

Images