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 includes 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 priority and the benefit of Korean Patent Application No. 10 - 2024 - 0001130, 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 same. Background art

[0004] Extreme ultraviolet (EUV) lithography has drawn 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 the EUV lithography technology, extremely fine patterns (e.g., less than or equal to 20 nanometers) can be formed in the exposure process during semiconductor device manufacturing.

[0005] The extreme ultraviolet (EUV) lithography technology is achieved by developing compatible photoresists that can be performed 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 characteristic roughness (also referred to as line edge roughness or LER).

[0006] The inherent image blur caused by the acid - catalyzed reaction 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, the light absorption rate of the photoresist at a wavelength of 13.5 nanometers is reduced, thereby reducing their sensitivity. Chemically amplified (CA) photoresists may face more difficulties in part under EUV exposure.

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

[0008] To address the drawbacks of the above-mentioned 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 composition removal through a non-chemically amplified mechanism. Such inorganic compositions contain inorganic elements with higher EUV absorption rates than hydrocarbon groups, so they can ensure sensitivity through a non-chemically amplified mechanism and may be less sensitive to random effects, thus having 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] The above materials are effective for large-pitch patterning in a bilayer configuration for far-ultraviolet (deep UV), X-ray, and electron beam light sources. Recently, when using a cationic hafnium metal oxide sulfate (HfSO x ) material together with a peroxo complexing agent to image a 15-nanometer half-pitch (HP) through projection EUV exposure, impressive performance has been obtained. The system exhibits the highest performance of non-CA photoresists and has a practical photosensitivity close to the required or desired level for EUV lithography. However, the hafnium metal oxide sulfate material with a peroxo complexing agent has some practical drawbacks. 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 and / 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 it would be beneficial to further improve the patterning characteristics for commercial availability. SUMMARY OF THE INVENTION

[0012] Some embodiments of the present disclosure provide a semiconductor photoresist composition with improved coating performance and sensitivity.

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

[0014] A 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.

[0015] Chemical Formula 1

[0016]

[0017] In Chemical Formula 1,

[0018] R 5 to R 7 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, a substituted or unsubstituted C7-C30 aralkyl group, a substituted or unsubstituted C1-C20 alkoxy group, -L a -X 1 -R a (wherein X 1 is O or S, L a is a single bond (e.g., a single covalent bond) or a substituted or unsubstituted C1-C20 alkylene group, and R a is hydrogen or a substituted or unsubstituted C1-C20 alkyl group), or -L b -N(R b )(R c )(wherein L b is a single bond (e.g., a single covalent bond) or a substituted or unsubstituted C1-C20 alkylene group, and R b and R c are each independently hydrogen or a substituted or unsubstituted C1-C20 alkyl group),

[0019] wherein, at least one of R 5 to R 7 is selected to be -L b -N(R b )(R c ).

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

[0021] The semiconductor photoresist composition according to some embodiments achieves excellent sensitivity and excellent coating properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The accompanying drawings, together with the specification, illustrate embodiments 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] Explanation of reference numerals in the drawings

[0025] 100: Substrate;

[0026] 102: Thin film;

[0027] 104: Antireflective bottom layer;

[0028] 106: Photoresist film;

[0029] 106a: Exposed area;

[0030] 106b: Unexposed area;

[0031] 108: Photoresist pattern;

[0032] 110: Patterning mask;

[0033] 112: Organic film pattern;

[0034] 114: Thin film pattern. Detailed description of specific embodiments

[0035] Hereinafter, embodiments of the present disclosure will be described in more detail with reference to the accompanying drawings. In the following description of the present disclosure, well-known functions or structures may not be described in order to clarify the subject matter of the present disclosure.

[0036] To clearly illustrate the subject matter of the present disclosure, certain descriptions and / or 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.

[0037] 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 when an element such as a layer, film, region, or substrate is referred to as being "on" another element, it may be directly on the other element or there may also be intervening elements.

[0038] 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-C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3-C30 saturated or unsaturated cycloaliphatic hydrocarbon group, or a substituted or unsubstituted C6-C30 aromatic hydrocarbon group), -SiRR'R" (wherein R, R' and R" are each independently hydrogen, a substituted or unsubstituted C1-C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3-C30 saturated or unsaturated cycloaliphatic hydrocarbon group, or a substituted or unsubstituted C6-C30 aromatic hydrocarbon group), a C1-C30 alkyl group, a C1-C10 haloalkyl group, a C1-C10 alkylsilyl group, a C3-C30 cycloalkyl group, a C6-C30 aryl group, a C1-C20 alkoxy group, a C1-C20 sulfide group, or a combination thereof. "Unsubstituted" means that the hydrogen atom is not replaced by another substituent and remains a hydrogen atom.

[0039] As used herein, when no other definition is provided, "alkyl" means a straight-chain or branched-chain aliphatic hydrocarbon group. The alkyl group can be a "saturated alkyl" that does not contain any double or triple bonds.

[0040] The alkyl group can be a C1-C8 alkyl group. For example, the alkyl group can be a C1-C7 alkyl group, a C1-C6 alkyl group, or a C1-C5 alkyl group. For example, a C1-C5 alkyl group can be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or 2,2-dimethylpropyl.

[0041] As used herein, when no other definition is provided, "cycloalkyl" means a monovalent cyclic aliphatic hydrocarbon group.

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

[0043] As used herein, "aliphatic unsaturated organic group" means a hydrocarbon group containing a bond, wherein the bond between one carbon atom and another carbon atom in the indicated molecule is a double bond, a triple bond, or a combination thereof.

[0044] The aliphatic unsaturated organic group may be a C2 to C8 aliphatic unsaturated organic group. For example, the aliphatic unsaturated organic group may 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 may 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-butenyl, 2-butenyl, 3-butenyl, 1-butynyl, 2-butynyl, or 3-butynyl.

[0045] As used herein, "aryl" refers to a substituent in which all atoms (or all ring atoms, e.g., all ring atoms except hydrogen and / or other substituents) in the cyclic substituent have p orbitals, and these p orbitals are conjugated, and may include monocyclic functional groups, polycyclic functional groups, or fused ring (e.g., rings sharing adjacent carbon atom pairs) functional groups.

[0046] As used herein, "heteroaryl" refers to an aryl containing at least one heteroatom selected from N, O, S, P, and Si. Two or more heteroaryls are directly connected by a σ bond, or when the heteroaryl includes two or more rings, two or more rings may be fused together. When the heteroaryl is a fused ring, each ring may contain one to four heteroatoms.

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

[0048] As used herein, unless otherwise defined, "alkynyl" refers to an aliphatic unsaturated alkynyl containing at least one triple bond as a straight-chain or branched-chain aliphatic hydrocarbon group.

[0049] Hereinafter, a semiconductor photoresist composition according to some embodiments will be described.

[0050] A 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.

[0051] Chemical Formula 1

[0052]

[0053] In Chemical Formula 1,

[0054] R 5 to R 7Each 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, a substituted or unsubstituted C7-C30 aralkyl group, a substituted or unsubstituted C1-C20 alkoxy group, L a -X 1 -R a (wherein X 1 is O or S, and L a is a single bond (e.g., a single covalent bond) or a substituted or unsubstituted C1-C20 alkylene group, and R a is hydrogen or a substituted or unsubstituted C1-C20 alkyl group), or -L b -N(R b )(R c )(wherein L b is a single bond (e.g., a single covalent bond), or a substituted or unsubstituted C1-C20 alkylene group, and R b and R c are each independently hydrogen or a substituted or unsubstituted C1-C20 alkyl group),

[0055] provided that at least one selected from R 5 to R 7 is -L b -N(R b )(R c ).

[0056] 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 0.001% by weight to about 10% by weight.

[0057] 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 0.005% by weight to about 10% by weight or about 0.01% by weight to about 5% by weight.

[0058] 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% by weight to about 30% by weight.

[0059] The semiconductor photoresist composition according to some embodiments can improve the sensitivity of the photoresist by including the Sn-containing organometallic compound and the carboxylic acid compound within the above content ranges.

[0060] According to some embodiments, the semiconductor photoresist composition may include an Sn-containing organometallic compound and a carboxylic acid compound in a weight ratio of about 99:1 to about 90:10. For example, the semiconductor photoresist composition may include an Sn-containing organometallic compound and the carboxylic acid compound represented by Chemical Formula 1 in a weight ratio of about 95:5 to about 90:10.

[0061] If the weight ratio of the Sn-containing organometallic compound and the carboxylic acid compound satisfies the above range, a semiconductor photoresist composition having excellent sensitivity can be provided.

[0062] The Sn-containing organometallic compound may include at least one group selected from an organic oxy group and an organic carbonyl oxy group.

[0063] The Sn-containing organometallic compound may be a compound represented by Chemical Formula 2 or a condensation compound thereof.

[0064] Chemical Formula 2

[0065]

[0066] In Chemical Formula 2,

[0067] R 8 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,

[0068] R 9 to R 11 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 an aryloxy group (-OR d , where R d 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 e , where R eis 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 f R 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 amido group (-NR h (COR i ) wherein R h and R i 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 j C(NR k )R l wherein R j 、R k and R l 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 an arylthio group (-SR m 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 / or a thiocarbonyl group (-S(CO)R n wherein 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

[0069] at least one from R 9 to R 11The selected group is selected from alkoxy and aryloxy (-OR d , where R d 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), carboxyl (-O(C=O)R e , where R e 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), alkylamide and / or dialkylamide (-NR f R g , where 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), amido (-NR h (C=OR i ), where R h and R i 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), amidino (-NR j C(NR k )R l , where R j , R k and R l 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), alkylthio and arylthio (-SR m , where 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 thiocarbonyl (-S(C=O)Rn , wherein 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).

[0070] In some embodiments, at least one selected from R 9 to R 11 may be selected from alkoxy and aryloxy (-OR d , wherein R d 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 carboxyl (-O(C=O)R e , wherein R e 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).

[0071] In an embodiment, the compound represented by Chemical Formula 2 includes -OR d or -OC(=O)R e as a ligand, such that a pattern formed using a semiconductor photoresist composition containing the same can exhibit excellent ultimate resolution.

[0072] In an embodiment, -OR d and / or -OC(=O)R e ligands can determine the solubility of the compound represented by Chemical Formula 2 in a solvent.

[0073] R 8 may 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,

[0074] R dmay 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

[0075] R e 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.

[0076] R 8 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,

[0077] R d 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

[0078] R e 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.

[0079] In the examples, the Sn-containing organometallic compound may be represented by Chemical Formula 3 or Chemical Formula 4.

[0080] Chemical Formula 3

[0081] R 12 z SnO (2-(z / 2)-(x / 2)) (OH) x

[0082] In Chemical Formula 3,

[0083] R 12 is a C1-C31 hydrocarbon group, where 0 < z ≤ 2 and 0 < (z + x) ≤ 4;

[0084] Chemical Formula 4

[0085] R 13n2 Sn m1 X l1 Y k1

[0086] Among them, in Chemical Formula 4,

[0087] R 13 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 including 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,

[0088] X is sulfur (S), selenium (Se), or tellurium (Te),

[0089] Y is -OR m or -OC(=O)R n ,

[0090] 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

[0091] 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

[0092] n2, m1, l1, and k1 are each independently an integer in the range of 1 to 20.

[0093] According to some embodiments, the solvent of the semiconductor photoresist composition can be an organic solvent, and for example, it can be an aromatic compound (e.g., xylene, toluene, etc.), alcohols (e.g., 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropanol, 1-propanol), ethers (e.g., anisole, tetrahydrofuran), esters (n-butyrate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate), ketones (e.g., methyl ethyl ketone, 2-heptanone), or a mixture thereof, but not limited thereto.

[0094] According to some embodiments, in addition to the above-mentioned Sn-containing organometallic compound, carboxylic acid compound, and solvent, the semiconductor photoresist composition may further include a resin.

[0095] The resin can be a phenolic resin containing at least one Group 2 aromatic group.

[0096] Group 2

[0097]

[0098] The resin can have a weight-average molecular weight of about 500 to about 20,000.

[0099] Based on the total amount of the semiconductor photoresist composition, the resin can be included in an amount of about 0.1 wt% to about 50 wt%.

[0100] If the resin is included in the above content range, it may have excellent etching resistance and heat resistance.

[0101] In an embodiment, the semiconductor photoresist composition can be composed of the above-mentioned Sn-containing organometallic compound, carboxylic acid compound, solvent, and resin.

[0102] However, the semiconductor photoresist composition according to the above embodiment can further include additives as needed or desired. Examples of the additives can be surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0103] The surfactant can include, for example, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycols, quaternary ammonium salts, or combinations thereof, but is not limited thereto.

[0104] The crosslinking agent can 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. The crosslinking agent can have 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 acrylate, 1,4-butanediol diglycidyl ether, glycidol, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, trimethylolpropane triglycidyl ether, 1,3-bis(glycidyloxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea, and / or analogs.

[0105] The leveling agent can be used to improve the coating flatness during the printing process and can be any suitable leveling agent commonly used in the art.

[0106] 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.

[0107] The quencher may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0108] In some embodiments, the semiconductor photoresist composition according to the present invention may be mixed with an acidic compound different from the above carboxylic acid compound. Examples of the acidic compound that can be mixed include organic acids, sulfonic acids, phosphonic acids, and the like.

[0109] The amount of the additive used can be controlled according to suitable or desired properties.

[0110] 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 (e.g., 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.

[0111] The semiconductor photoresist composition can be formed into a pattern with a high aspect ratio without collapsing. Therefore, in order to form a fine pattern having a width of, for example, about 5 nm to about 100 nm, such as about 5 nm to about 80 nm, such as about 5 nm to about 70 nm, such as about 5 nm to about 50 nm, such as about 5 nm to about 40 nm, such as about 5 nm to about 30 nm, or such as about 5 nm to about 20 nm, the semiconductor photoresist composition can be used in a lithography process using light with a wavelength range of about 5 nm to about 150 nm, such as about 5 nm to about 100 nm, about 5 nm to about 80 nm, about 5 nm to about 50 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm. Therefore, the semiconductor photoresist composition according to some embodiments can be used to achieve extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5 nm.

[0112] According to some embodiments, a method of forming a pattern using the above semiconductor photoresist composition is provided. For example, the fabricated pattern may be a photoresist pattern.

[0113] A 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 film, patterning the photoresist film to form a photoresist pattern, and etching the etching target film using the photoresist pattern as an etching mask.

[0114] Hereinafter, with reference to Figures 1 - 5 a method of forming a pattern using a semiconductor photoresist composition will be described. Figures 1 - 5 is a cross-sectional view for explaining a method of forming a pattern using a semiconductor photoresist composition according to some embodiments.

[0115] With reference to Figure 1 , an object for etching is prepared. The object for etching may be a thin film 102 on a semiconductor substrate 100. Hereinafter, the object for etching is defined as the thin film 102, but the present disclosure is not limited thereto. 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.

[0116] Subsequently, a resist underlayer composition for forming a resist underlayer 104 is spin-coated on the surface of the cleaned thin film 102. However, this embodiment is 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 the like.

[0117] The coating process of the resist underlayer may be omitted, and the following description includes the process of coating the resist underlayer.

[0118] 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).

[0119] The resist underlayer 104 is located between the substrate 100 and the photoresist film 106. Therefore, when light reflected from the interface between the substrate 100 and the photoresist film 106 and / or a hard mask between the layers scatters into an unintended photoresist region, non-uniformity can be prevented or reduced and the pattern formation ability of the photoresist line width can be improved.

[0120] With reference to Figure 2 , a photoresist film 106 is formed by coating a semiconductor photoresist composition on the resist underlayer 104. The photoresist film 106 is obtained by coating the above-mentioned semiconductor photoresist composition on the thin film 102 on the substrate 100 and then curing it by heat treatment.

[0121] In an embodiment, forming a pattern using a semiconductor photoresist composition may include coating the semiconductor photoresist composition on a substrate 100 having a thin film 102 by methods such as spin coating, slot coating, inkjet printing, etc., and then drying it to form a photoresist film 106.

[0122] The semiconductor photoresist composition has been described in detail above and may not be described or illustrated herein again.

[0123] Subsequently, the substrate 100 having the photoresist film 106 undergoes a first baking process. The first baking process may be performed at a temperature of about 80 °C to about 120 °C.

[0124] Referring to Figure 3 , the photoresist film 106 may be selectively exposed using a patterning mask 110.

[0125] For example, the exposure may 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 light having 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).

[0126] In an embodiment, the exposure light according to some embodiments may have a short wavelength range of about 5 nm to about 150 nm and a high energy wavelength, such as EUV (extreme ultraviolet; wavelength 13.5 nm), electron beam (E - Beam), and / or similar light.

[0127] The exposed area 106a of the photoresist film 106 and the unexposed area 106b of the photoresist film 106 have different solubilities, which is achieved by forming a polymer formed through a cross - linking reaction (such as a condensation reaction) between organometallic compounds.

[0128] Subsequently, the substrate 100 undergoes a second baking process. The second baking process may 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 film 106 becomes insoluble to the developer.

[0129] In Figure 4 , a developer is used to dissolve and remove the unexposed area 106b of the photoresist film to form a photoresist pattern 108. For example, the unexposed area 106b of the photoresist film is dissolved and removed by using an organic solvent such as 2 - heptanone and / or the like to complete the photoresist pattern 108 corresponding to a negative image.

[0130] As described above, the developer used in the method of forming a pattern according to some embodiments may be an organic solvent. The organic solvent used in the method of forming a pattern according to some embodiments may 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 combinations thereof.

[0131] However, the photoresist pattern according to some embodiments is not limited to a negative image, but may be formed to have a positive tone image. Here, the developer for forming a positive image may be a quaternary ammonium hydroxide composition such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof.

[0132] As described above, exposure to light having high energy such as extreme ultraviolet (EUV; wavelength 13.5 nm), electron beam (E-Beam), and / or the like, and light having a relatively long wavelength such as i-line (wavelength about 365 nm), KrF excimer laser (wavelength about 248 nm), ArF excimer laser (wavelength about 193 nm), and / or the like, can provide a photoresist pattern 108 having a width thickness of about 5 nm to about 100 nm. For example, the photoresist pattern 108 may have a width thickness of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm.

[0133] In an embodiment, the photoresist pattern 108 may have a pitch of less than or equal to about 50 nm, such as less than or equal to about 40 nm, such as less than or equal to about 30 nm, such as less than or equal to about 20 nm, or such as less than or equal to about 15 nm, and a line width roughness of less than or equal to about 10 nm, less than or equal to about 5 nm, less than or equal to about 3 nm, or less than or equal to about 2 nm.

[0134] In an embodiment, the photoresist pattern 108 is used as an etch mask to etch the underlying resist 104. 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.

[0135] Refer to Figure 5 , 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.

[0136] The etching of the thin film 102 can be, for example, dry etching using an etching gas, and the etching gas can be, for example, CHF3, CF4, Cl2, BCl3, or a mixed gas thereof.

[0137] 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 can have a width corresponding to the photoresist pattern 108. For example, the thin film pattern 114 can have a width of 5 nm to 100 nm 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 can have a width of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm, or for example, a width less than or equal to about 20 nm, just like the width of the photoresist pattern 108.

[0138] After that, embodiments of the present disclosure will be described in more detail by the preparation examples of the above semiconductor photoresist composition. However, the present disclosure is not technically limited by the following examples.

[0139] Synthesis of Organometallic Compounds

[0140] Synthesis Example 1

[0141] In a 250 mL two-necked round-bottom flask, 40.7 g of t-butyltin triphenyl (t-butylSnPh3) and 300 g of propionic acid were added, and then heated under reflux for 24 hours.

[0142] The unreacted propionic acid was removed under reduced pressure to obtain the compound represented by Chemical Formula 5.

[0143] Chemical Formula 5

[0144]

[0145] Synthesis Example 2

[0146] 30 mL of anhydrous pentane was added to 10 g of t-Amyltin trichloride (t-AmylSnCl3), then maintained at 0 °C, and 7.4 g of diethylamine and 6.1 g of ethanol were added thereto, and then 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.

[0147] Chemical Formula 6

[0148]

[0149] Synthesis Example 3

[0150] Dissolve 10 g of dibutyltin chloride in 30 mL of diethyl ether. Add 70 mL of 1 M aqueous sodium hydroxide (NaOH) solution thereto, and then stir for 1 hour. After stirring, filter the solid produced therein, wash it three times with 25 mL of deionized water, and dry it under reduced pressure at 100 °C to obtain an organometallic compound represented by Chemical Formula 7, having a weight-average molecular weight of 1,500.

[0151] Chemical Formula 7

[0152]

[0153] Preparation of Semiconductor Photoresist Composition

[0154] Examples 1 to 3 and Comparative Examples 1 to 5

[0155] The compounds represented by Chemical Formulas 5 to 7 according to Synthesis Examples 1 to 3 and a carboxylic acid compound were dissolved in propylene glycol methyl ether acetate (PGMEA) at the respective weight ratios shown in Table 1 at a concentration of 3 wt%, and then filtered through a 0.1-μm polytetrafluoroethylene (PTFE) syringe filter to prepare semiconductor photoresist compositions according to Examples 1 to 3 and Comparative Examples 1 to 5.

[0156] Table 1

[0157]

[0158] Evaluation 1: Evaluation of Sensitivity and Line Edge Roughness (LER)

[0159] Each of the semiconductor photoresist compositions according to the examples and comparative examples was spin-coated on a 200-mm circular silicon wafer 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.

[0160] Subsequently, on a wafer coated with a photoresist composition, a line array consisting of 50 circular pads, each with a diameter of 500 microns, was projected using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). Here, the exposure time of the pads was adjusted to apply an increasing EUV dose to each pad.

[0161] Subsequently, the photoresist and the substrate were exposed on a hot plate at 160 °C for 120 seconds and then baked. The baked film was developed with propylene glycol monomethyl ether acetate solvent to form a negative image. Finally, the hot plate was baked at 150 °C for 2 minutes to complete the process.

[0162] The remaining photoresist thickness of the exposed pads was measured using an ellipsometer. The sensitivity was measured by measuring the remaining thickness for each exposure dose and plotting it as a function of the exposure dose on a graph, and the line edge roughness (LER) was measured from field-emission scanning electron microscope (FE-SEM) images. The sensitivity and line edge roughness were evaluated according to the following criteria, and the results are shown in Table 2.

[0163] Sensitivity evaluation criteria

[0164] -A: Less than 16 mJ / cm²

[0165] -B: Greater than or equal to 16 mJ / cm²

[0166] LER evaluation criteria

[0167] -○: Less than or equal to 2 nm

[0168] -△: Greater than 2 nm and less than or equal to 5 nm

[0169] -X: Greater than 5 nm

[0170] Evaluation 2: Surface roughness evaluation

[0171] Each photoresist composition according to Examples 1 to 3 and Comparative Examples 1 to 5 was spin-coated on a wafer at 1500 revolutions per minute for 60 seconds and baked at 110 °C for 60 seconds to form a thin film. Images were taken using an atomic force microscope (AFM), etc., and the surface roughness of the thin film was measured using software (such as an optical profiler) according to the following criteria. The results are shown in Table 2.

[0172] In surface roughness, the root mean square roughness (R q ) refers to the root mean square (rms) of the lengths within the reference length of the roughness profile.

[0173] Surface roughness evaluation criteria

[0174] –○:R q Less than 0.4

[0175] –X:R q Greater than or equal to 0.4

[0176] Table 2

[0177] Sensitivity LER Surface roughness Example 1 A ○ ○ Example 2 A ○ ○ Example 3 A ○ ○ Comparative Example 1 A X X Comparative Example 2 A △ X Comparative Example 3 A ○ X Comparative Example 4 B X X Comparative Example 5 B △ X

[0178] Referring to the results in Table 2, compared with the patterns formed using the semiconductor photoresist compositions according to Comparative Examples 1 to 5 respectively, the patterns formed using the semiconductor photoresist compositions according to Examples 1 to 3 respectively exhibit excellent sensitivity and improved line edge roughness and coating properties.

[0179] Previously, exemplary embodiments of the present disclosure 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, such 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 appended claims 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, R 5 to R 7 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, a substituted or unsubstituted C7-C30 aralkyl group, a substituted or unsubstituted C1-C20 alkoxy group, -L a -X 1 -R a 、or -L b -N(R b )(R c ), where X 1 is O or S, L a is a single bond or a substituted or unsubstituted C1-C20 alkylene group, and R a is hydrogen or a substituted or unsubstituted C1-C20 alkyl group, where L b is a single bond or a substituted or unsubstituted C1-C20 alkylene group, and R b and R c each independently is hydrogen or a substituted or unsubstituted C1-C20 alkyl group, Provided that at least one selected from R 5 to R 7 is -L b -N(R b )(R c ).

2. The semiconductor photoresist composition according to claim 1, wherein: Based on 100% by weight of the semiconductor photoresist composition, the carboxylic acid compound is included in an amount of 0.001% to 10% by weight.

3. The semiconductor photoresist composition according to claim 1, wherein: Based on 100% by weight of the semiconductor photoresist composition, the carboxylic acid compound is included in an amount of 0.01% to 5% by weight.

4. 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.

5. The semiconductor photoresist composition according to claim 1, wherein: The weight ratio of the included Sn-containing organometallic compound to the carboxylic acid compound is 99:1 to 90:

10.

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

7. The semiconductor photoresist composition according to claim 1, wherein: The Sn-containing organometallic compound includes at least one selected from an organic oxy group and an organic carbonyl oxy group.

8. The semiconductor photoresist composition according to claim 1, wherein: The Sn-containing organometallic compound is a compound represented by Chemical Formula 2 or its condensate: [Chemical Formula 2] Wherein, in Chemical Formula 2, R 8 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 9 to R 11 are each independently 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 d ), where R d 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 e ), where R e 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 and / or a dialkylamide (-NR f R g ), where 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 amide group (-NR h (COR i ))), where R h and R i 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 j C(NR k )R l ), where R j , R k and R l 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 m ), 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 / or a thiocarbonyl group (-S(CO)R n ), wherein 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 R 9 to R 11 at least one selected from alkoxy and aryloxy (-OR d ), where R d 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 e ), where R e 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 f R 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; amido (-NR h (C=OR i ))), where R h and R i 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 j C(NR k )R l ), where R j , R k and R l 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 m ), where 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 a thiocarbonyl group (-S(C=O)R n ), where 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.

9. The semiconductor photoresist composition according to claim 8, wherein Selected from R 9 to R 11 At least one selected from alkoxy and aryloxy (-OR d ), where R d 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 carboxy (-O(C=O)R e ), where R e 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.

10. The semiconductor photoresist composition according to claim 8, wherein R 8 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 d 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 e 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.

11. 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 12 z SnO (2-(z / 2)-(x / 2)) (OH) x Among them, In Chemical Formula 3, R 12 is a C1 to C31 hydrocarbon group, where 0 < z ≤ 2, 0 < (z + x) ≤ 4; [Chemical Formula 4] R 13 n2 Sn m1 X l1 Y k1 Wherein, in Chemical Formula 4, R 13 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 including 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 oxopropyl group, or a combination thereof. X is sulfur (S), selenium (Se), or tellurium (Te), 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 n2, m1, l1, and k1 are each independently an integer in the range of 1 to 20.

12. A method of forming a pattern, comprising: providing an etching target film on a substrate; coating the semiconductor photoresist composition according to any one of claims 1 to 11 on the etching target film to form a photoresist film; patterning the photoresist film to form a photoresist pattern; and using the photoresist pattern as an etching mask to etch the etching target film.

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