Semiconductor photoresist composition and method of forming pattern using the same

Abstract

The semiconductor photoresist composition comprises an organic metal compound; an organic solvent including a ketone solvent; and an organic acid compound. A method of forming a pattern using a semiconductor photoresist composition is disclosed.

Description

[0001] Cross-reference of related applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2024-0115270, filed on August 27, 2024, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This invention relates to a semiconductor photoresist composition and a method for forming patterns thereon. Background Technology

[0004] Extreme ultraviolet (EUV) lithography has attracted attention as an important (e.g., necessary or desirable) technology for manufacturing next-generation semiconductor devices. EUV lithography is a patterning technique that uses EUV rays with a wavelength of 13.5 nanometers as the exposure source. In EUV lithography, extremely fine patterns (e.g., less than or equal to 20 nanometers) can be formed through exposure processes during the fabrication of semiconductor devices.

[0005] The realization of extreme ultraviolet (EUV) lithography depends on the development of compatible photoresists that can achieve spatial resolutions of 16 nanometers or less. Currently, efforts are underway to overcome the limitations of chemically amplified (CA) photoresists in terms of resolution, sensitivity, and / or feature roughness (also known as line edge roughness or LER) to meet the specifications of next-generation devices.

[0006] The inherent image blurring caused by acid-catalyzed reactions in these polymeric photoresists has long been known to limit the resolution of small feature sizes in electron beam lithography. Chemically amplified (CA) photoresists are designed for high sensitivity, but their typical elemental composition reduces light absorption at 13.5 nm wavelengths and thus reduces their sensitivity, making their use under EUV exposure more difficult.

[0007] Furthermore, CA photoresists may present challenges at small feature sizes due to roughness issues. Experimental results show that the line edge roughness (LER) of CA photoresists increases with decreasing sensitivity, partly due to the inherent characteristics of acid catalyst processes. Therefore, the semiconductor industry needs (e.g., demands) novel, high-performance photoresists to address these shortcomings and problems of CA photoresists.

[0008] To overcome the drawbacks of chemically amplified (CA) organic photoresist compositions, inorganic photoresist compositions have been investigated. Inorganic photoresist compositions are primarily used for negative patterning and have resistance to removal by developer compositions due to chemical modification by a non-chemically amplified mechanism. Inorganic compositions contain inorganic elements with higher EUV absorption rates than hydrocarbons and thus can ensure proper sensitivity by a non-chemically amplified mechanism. In addition, inorganic compositions are less sensitive to stochastic effects and thus can have low line edge roughness and fewer defects.

[0009] Inorganic photoresists based on peroxopolyacids of tungsten mixed with tungsten, niobium, titanium and / or tantalum have been reported as radiation-sensitive materials for patterning (see, US 5061599; and H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298-300, 1986, the entire contents of which are hereby incorporated by reference).

[0010] These materials are effectively used for patterning large-pitch applications in bilayer configurations, such as far-ultraviolet (deep UV), X-ray, and electron beam sources. Recently, impressive performance has been achieved in imaging 15 nm half-pitch (HP) images via projection EUV exposure using cationic hafnium oxide sulfate (HfSOx) materials with peroxy miscible agents (see, US2011-0045406; and JK Stowers, A. Telecky, M. Kocsis, BL Clark, DA Keszler, A. Grenville, CN Anderson, PP Naulleau, Proceedings of the International Society for Optical Engineering (Proc. SPIE), 7969, 796915, 2011, the entire contents of which are incorporated herein by reference). This system exhibits optimal performance for non-CA photoresists and offers feasible photosensitivity close to that required for EUV photoresists. However, hafnium metal oxide sulfate materials with peroxide miscible agents have several practical drawbacks. First, these materials are coated in a mixture of corrosive sulfuric acid / hydrogen peroxide and may have insufficient shelf-life stability. Second, as a complex mixture, structural modifications for performance improvement are not readily available. Third, development must be performed in a tetramethylammonium hydroxide (TMAH) solution at a high (e.g., extremely high) concentration of 25% by weight and / or similar.

[0011] Recently, tin-containing molecules (e.g., materials) with excellent or adequate extreme ultraviolet absorption have been actively studied. Among these molecules, organotin polymers achieve negative patterning resistant to organic developer removal by crosslinking with adjacent chains via oxo bonds through photoabsorption or secondary electron dissociation of alkyl ligands. These organotin polymers exhibit significantly improved sensitivity while maintaining adequate resolution and line edge roughness, but their patterning properties require further improvement for commercial applications. Summary of the Invention

[0012] One aspect of certain embodiments is directed to a semiconductor photoresist composition having enhanced (e.g., improved) sensitivity and exposure delay characteristics.

[0013] One aspect of certain embodiments is a method for forming patterns using semiconductor photoresist compositions.

[0014] Other aspects will be set forth in part in the description which follows, and in part will be obvious from the description or may be learned by practice of the embodiments disclosed.

[0015] Semiconductor photoresist compositions according to certain embodiments include organometallic compounds, organic solvents including ketone solvents, and organic acid compounds.

[0016] The method of forming a pattern according to certain embodiments includes forming an etch target layer on a substrate, coating a semiconductor photoresist composition on the etch target layer to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and using the photoresist pattern as an etch mask to etch the etch target layer.

[0017] Semiconductor photoresist compositions according to certain embodiments can improve surface roughness by enhancing coating properties and providing photoresist patterns with improved humidity and thermal stability. For example, semiconductor photoresist compositions can improve surface roughness by enhancing the coating properties of the photoresist layer. This enhancement results in the formation of photoresist patterns with superior humidity and thermal stability, maintaining pattern integrity during subsequent process steps (e.g., operation or task). Improved humidity and thermal stability ensure that the photoresist pattern remains intact and accurate even under challenging environmental conditions, thereby contributing to the overall reliability and performance of the semiconductor device. Attached Figure Description

[0018] The accompanying drawings are included to provide a further understanding of this disclosure and are incorporated in and form a part of this specification. The drawings illustrate embodiments of the disclosure and, together with the description, serve to explain the principles of the disclosure. In the drawings:

[0019] Figures 1A-1E A cross-sectional view illustrating a method for forming patterns using semiconductor photoresist compositions according to certain example embodiments.

[0020] Explanation of icon numbers

[0021] 100: Substrate

[0022] 102:Film

[0023] 104: Resist underlayer

[0024] 106: Photoresist layer

[0025] 106a: Unexposed area

[0026] 106b: Exposure Area

[0027] 108: Pattern

[0028] 110: Patterned Mask

[0029] 112: Organic layer pattern

[0030] 114: Thin Film Pattern Detailed Implementation

[0031] Hereinafter, embodiments will be described in more detail with reference to the accompanying drawings. In the following description of this disclosure, functions or structures known to those skilled in the art will not be described in order to clarify this disclosure.

[0032] Throughout this disclosure, identical or similar configuration components are indicated by the same reference numerals. Furthermore, since the size and thickness of each configuration shown in the figures are arbitrarily depicted for better understanding and ease of illustration, this disclosure is not necessarily limited thereto.

[0033] In the accompanying drawings, the thickness of layers, films, panels, regions, etc., is exaggerated for clarity. The thickness of a portion of a layer or region is also exaggerated for clarity in the accompanying drawings. It should be understood that when a component (e.g., a layer, film, region, or substrate) is referred to as being "on" another component, the component may be directly on the other component, or there may be intermediate components present.

[0034] As used herein, the term "substituted" refers to a hydrogen atom substituted with a deuterium, halogen, hydroxyl, carboxyl, thiol, cyano, nitro, -NRR' (where R and R' can each independently be hydrogen, substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), or -SiRR'R"" (where R, R', and R"" can each independently be hydrogen, substituted or unsubstituted C1 to C30 saturated or unsaturated alicyclic hydrocarbon group, or substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), or -SiRR'R"" (where R, R', and R"" can each independently be hydrogen, substituted or unsubstituted C1 to C30 saturated or unsaturated alicyclic hydrocarbon group, or substituted or unsubstituted C6 to C30 aromatic hydrocarbon group). The substituents include hydrogen, substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon groups, substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon groups, or substituted or unsubstituted C6 to C30 aromatic hydrocarbon groups, C1 to C30 alkyl groups, C1 to C10 haloalkyl groups, C1 to C10 alkylsilyl groups, C3 to C30 cycloalkyl groups, C6 to C30 aryl groups, C1 to C20 alkoxy groups, C1 to C20 sulfide groups, and / or (e.g., any suitable combination thereof). The term "unsubstituted" means that the hydrogen atom is not substituted by another substituent and remains a hydrogen atom.

[0035] As used herein, unless otherwise defined (e.g., when), the term "alkyl" refers to a linear or branched aliphatic hydrocarbon group. An alkyl group may be a "saturated alkyl" that does not have any double or triple bonds.

[0036] The alkyl group can be C1 to C8 alkyl. For example, the alkyl group can be C1 to C7 alkyl, C1 to C6 alkyl, or C1 to C5 alkyl. For example, C1 to C5 alkyl can be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or 2,2-dimethylpropyl.

[0037] As used herein, unless otherwise defined, the term “cycloalkyl” refers to a monovalent cyclic aliphatic hydrocarbon group.

[0038] The cycloalkyl group can be C3 to C8 cycloalkyl, such as C3 to C7 cycloalkyl, C3 to C6 cycloalkyl, C3 to C5 cycloalkyl, or C3 to C4 cycloalkyl. For example, the cycloalkyl group can be cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl, but this disclosure is not limited thereto.

[0039] As used herein, the term "aryl" refers to a cyclic substituent in which all atoms have p-orbitals and these p-orbitals are conjugated, and may include monocyclic or fused-ring polycyclic (i.e., rings sharing adjacent carbon atom pairs) functional groups.

[0040] As used herein, the term "heteroaryl" may refer to an aryl group comprising at least one heteroatom selected from N, O, S, P, and Si. Two or more heteroaryl groups may be directly linked by σ bonds, or if (e.g., when) a heteroaryl group comprises two or more rings, the two or more rings may be fused. If (e.g., when) a heteroaryl group is a fused ring, each ring may comprise one to three heteroatoms.

[0041] As used herein, unless otherwise defined, the term "alkenyl" refers to an aliphatic unsaturated alkenyl group comprising at least one double bond as a linear or branched aliphatic hydrocarbon group.

[0042] As used herein, unless otherwise defined, the term "alkynyl" refers to an aliphatic unsaturated alkynyl group that includes at least one triple bond as a linear or branched aliphatic hydrocarbon group.

[0043] The following describes semiconductor photoresist compositions according to some example embodiments.

[0044] Semiconductor photoresist compositions according to some example embodiments include organometallic compounds, organic solvents including ketone solvents, and organic acid compounds.

[0045] The organic solvents included in the semiconductor photoresist composition according to the present disclosure include ketone solvents, and cross-linking bonds (e.g., promoting the formation of cross-linked structures) and entanglement can be induced by forming coordination bonds with multiple organometallic compounds through unshared electron pairs of oxygen atoms included in the ketone functional groups.

[0046] Therefore, using organic solvents is advantageous not only for increasing adsorption to the substrate but also for forming amorphous thin films.

[0047] Furthermore, because cross-linking and entanglement compensate for insufficient coordination number, stability to moisture and / or oxygen is improved, preventing or reducing precipitation due to hydration even during long-term storage, and preventing or reducing deformation or degradation due to air even when left unattended after coating (e.g., when) the coating is applied. In other words, the stability of the semiconductor photoresist composition during long-term storage and the stability of the film formed by coating the semiconductor photoresist composition are both improved due to the ketone solvent.

[0048] Ketone solvents may have chain (e.g., linear) or ring (e.g., cyclic) structures and may be represented, for example, by chemical formula 1 or chemical formula 2.

[0049] [Chemical Formula 1]

[0050]

[0051] In chemical formula 1,

[0052] R 1 and R 2 Each can be an independently substituted or unsubstituted C1 to C10 alkyl group;

[0053] [Chemical Formula 2]

[0054]

[0055] In chemical formula 2,

[0056] Cycle A can be a substituted or unsubstituted C3 to C10 cycloalkyl group.

[0057] For example, ketone solvents can be represented by the chain structure of chemical formula 1.

[0058] For example, a ketone solvent represented by chemical formula 1 can be represented by any of chemical formulas 1-1 to 1-4.

[0059]

[0060] In chemical formulas 1-1 to 1-4

[0061] R 1a It can be a substituted or unsubstituted methyl group.

[0062] R 1b It can be a substituted or unsubstituted ethyl group.

[0063] R 1c It can be substituted or unsubstituted propyl.

[0064] R 1d It can be substituted or unsubstituted butyl.

[0065] R 3 It can be a substituted or unsubstituted methyl group.

[0066] n1 can be any integer from 1 to 7.

[0067] n2 can be any integer from 1 to 6.

[0068] n3 can be any integer from 1 to 5.

[0069] n4 can be any integer from 1 to 4, and

[0070] R 4 and R 5 It may be hydrogen, halogen, substituted or unsubstituted C1 to C5 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C6 to C12 aryl, and / or (e.g., any suitable combination thereof) independently.

[0071] In some embodiments, n1 may be one of the integers from 1 to 5, n2 may be one of the integers from 1 to 4, n3 may be one of the integers from 1 to 3, and n4 may be 1 or 2.

[0072] In some embodiments, the ketone solvent represented by Formula 1 may be represented by any one of Formulas 1-1 to 1-3.

[0073] n1 can be any integer from 1 to 3, n2 can be 1 or 2, and n3 can be 1.

[0074] In some embodiments, the ketone solvent represented by Formula 1 may be represented by Formula 1-1 or Formula 1-2.

[0075] n1 can be 1 or 2, and n2 can be 1.

[0076] In some embodiments, the number of carbon atoms attached to the ketone functional group in Formula 1 may be from about 4 to about 10. In this case, the ketone solvent represented by Formula 1 may be, for example, pentanone, hexanone, heptanone, octanone, nonanone, decanone, undecanone, and / or the like.

[0077] In some embodiments, the number of carbon atoms attached to the ketone functional group in Formula 1 may be 4 to 8. In this case, the ketone solvent represented by Formula 1 may be, for example, pentanone, hexanone, heptanone, octanone, nonanone, and / or the like.

[0078] In some embodiments, the number of carbon atoms attached to the ketone functional group in Formula 1 may be 4 to 6. In this case, the ketone solvent represented by Formula 1 may be, for example, pentanone, hexanone, heptanone, and / or the like.

[0079] In some embodiments, the number of carbon atoms attached to the ketone functional group in Formula 1 may be 4 or 5. In this case, the ketone solvent represented by Formula 1 may be, for example, pentanone, hexanone, and / or the like.

[0080] In some embodiments, the ketone solvent represented by Formula 1 may be pentanone.

[0081] Organic solvents, including ketone solvents, may further include acetate solvents.

[0082] Including acetate solvents can improve coating uniformity and coating thickness stability.

[0083] Ketone solvents and acetate solvents may be included in a weight ratio of about 99:1 to about 50:50.

[0084] In some embodiments, ketone solvents and acetate solvents may be comprised in a weight ratio of about 99:1 to about 80:20 or about 90:10 to about 70:30.

[0085] Examples of acetate solvents include propylene glycol methyl ether acetate (PGMEA), ethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyllactate (EL), butyllactate (n-butylactate), 2-hydroxyethyl propionate, 2-hydroxy-2-methylethylpropionate, ethoxyethyl acetate, hydroxyethylacetate, methyl 2-hydroxy-3-methylbutanoic acidmethyl, 3-methoxymethyl propionate, 3-methoxyethylpropionate, 3-ethoxyethyl propionate, and 3-ethoxymethylpropionate. The following are listed as compounds: propionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, methyl 2-hydroxyisobutyrate, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate, and / or mixtures thereof (e.g., any suitable mixtures), but this disclosure is not limited thereto.

[0086] The boiling points of organic solvents, including ketone solvents, can be from about 100 degrees Celsius to about 160 degrees Celsius.

[0087] When the boiling point is within the above range, a substantially uniform film can be formed due to appropriate or suitable volatility during the coating process, and surface inhomogeneities such as pinholes caused by the evaporation of residual organic solvents after the drying or soft baking process can be minimized or reduced.

[0088] Organic solvents, including ketone solvents, may be included in an amount from about 70% to about 99.5% by weight, based on 100% by weight of the semiconductor photoresist composition.

[0089] Organometallic compounds may be included in amounts from about 0.5% to about 30% by weight, based on 100% by weight of the semiconductor photoresist composition.

[0090] The organic acid compound may be p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, fluorinated sulfonium salt, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, and / or combinations thereof (e.g., any suitable combination), but this disclosure is not limited thereto.

[0091] Organic acid compounds may be included in an amount from about 0.01 to about 20% by weight, based on 100% by weight of the semiconductor photoresist composition.

[0092] For example, organic acid compounds may be included in amounts of about 0.01 to about 10% by weight, about 0.02 to about 10% by weight, about 0.03 to about 10% by weight, or about 0.05 to about 10% by weight, based on 100% by weight of the semiconductor photoresist composition.

[0093] According to some example embodiments, semiconductor photoresist compositions can improve photoresist sensitivity by including organometallic compounds, ketone solvents, and organic acid compounds within the above-mentioned content (e.g., amount) range.

[0094] Organometallic compounds may be organotin compounds comprising at least one organic oxygen or organic carbonyl oxygen.

[0095] For example, organometallic compounds can be represented by chemical formula 3.

[0096] [Chemical Formula 3]

[0097]

[0098] In chemical formula 3,

[0099] R 6 It can be selected from substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and substituted or unsubstituted C7 to C30 aralkyl.

[0100] R 7 To R 9 Each can independently be a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, a substituted or unsubstituted C7 to C30 aralkyl, an alkoxy, or an aryloxy (-OR) b , where R b It can be a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl and / or (e.g., any suitable combination), or a carboxyl group (-O(CO)R). c , where R c It may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl and / or (e.g., any suitable combination), alkylamide or dialkylamide (-NR) d R e , where R d and R e Each can independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl and / or (e.g., any suitable combination), amide (-NR) f (COR g ), where Rf and R g Each can independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl and / or (e.g., any suitable combination), amidine (-NR) h C(NR i )R j , where R h R i and R j Each can independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl and / or (e.g., any suitable combination), alkylthio and arylthiol (-SR) k , where R k It may be a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl and / or (e.g., any suitable combination), or a thiocarboxyl (-S(CO)R) l , where R l It may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl and / or (e.g., any suitable combination), and

[0101] R 7 To R 9 At least one of them can be derived from alkoxy and aryloxy (-OR) b , where R b It can be a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl and / or (e.g., any suitable combination), or a carboxyl group (-O(CO)R). c , where R cIt can be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl and / or (e.g., any suitable combination), alkylamide and dialkylamide (-NR) d R e , where R d and R e Each can independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl and / or (e.g., any suitable combination), amide (-NR) f (COR g ), where R f and R g Each can independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl and / or (e.g., any suitable combination), amidine (-NR) h C(NR i )R j , where R h R i and R j Each can independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl and / or (e.g., any suitable combination), alkylthio and arylthiol (-SR) k , where R k It can be a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl and / or (e.g., any suitable combination), and a thiocarboxyl (-S(CO)R) l , where R lIt may be selected from hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl and / or (e.g., any suitable combination).

[0102] In one or more embodiments, R 7 To R 9 At least one of them can be derived from alkoxy and aryloxy (-OR) b , where R a It can be a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl and / or (e.g., any suitable combination), and a carboxyl group (-O(CO)R). c , where R c It may be selected from hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl and / or (e.g., any suitable combination).

[0103] In one or more embodiments, the compound represented by Formula 3 includes -OR b or -OC(=O)R c As a ligand, it enables patterns formed using semiconductor photoresist compositions containing this compound to exhibit excellent or suitable limiting resolution.

[0104] In addition, -OR b or -OC(=O)R c The ligands can affect or determine the solubility of compounds represented by chemical formula 3 in solvents.

[0105] In one or more embodiments, R 6 It may be a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 aliphatic unsaturated organogroup including one or more double or triple bonds, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C4 to C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, and / or (e.g., any suitable) combination thereof.

[0106] R bmay 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 and / or (e.g., any suitable) combination, and

[0107] 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 and / or (e.g., any suitable) combination.

[0108] In one or more embodiments, R 6 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 and / or (e.g., any suitable) combination,

[0109] 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 and / or (e.g., any suitable) combination, and

[0110] 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 and / or (e.g., any suitable) combination.

[0111] In one or more embodiments, the Sn-containing organometallic compound may be represented by Chemical Formula 4 or Chemical Formula 5.

[0112] [Chemical Formula 4]

[0113] R 10 z SnO (2-(z / 2)-(x / 2)) (OH) x

[0114] In Chemical Formula 4,

[0115] R 10 may be a C1-C31 hydrocarbon group, 0 < z ≤ 2, and 0 < (z + x) ≤ 4;

[0116] [Chemical Formula 5]

[0117] R 11 a Sn b X c Y d

[0118] In chemical formula 5,

[0119] R 11 It may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 aliphatic unsaturated organogroup including one or more double or triple bonds, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, and / or (e.g., any suitable) combination thereof.

[0120] X can be sulfur (S), selenium (Se), or tellurium (Te).

[0121] Y can be -OR m or -OC(=O)R n ,

[0122] R m It may be a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, and / or (e.g., any suitable combination).

[0123] R n It may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl and / or (e.g., any suitable combination), and

[0124] a, b, c, and d can each be an integer from 1 to 20 independently.

[0125] In some example embodiments, in addition to the aforementioned organometallic compounds and ketone solvents, the semiconductor photoresist composition may further include a resin.

[0126] The resin may be a phenolic resin, including at least one aromatic portion listed in Group 1 (e.g., selected from there).

[0127] [Group 1]

[0128]

[0129] The resin may have a weight average molecular weight of about 500 to about 20,000.

[0130] The resin may be included in an amount from about 0.1% to about 50% by weight, based on the total amount of the semiconductor photoresist composition.

[0131] If (for example, when) the resin is included in the above-mentioned content (e.g., amount) range, the semiconductor photoresist composition may have excellent or suitable etch resistance and heat resistance.

[0132] In one or more embodiments, the semiconductor photoresist composition may consist of the aforementioned organometallic compounds, organic solvents including ketone solvents, organic acid compounds, and resins.

[0133] However, the embodiments disclosed herein are not limited thereto, and the semiconductor photoresist composition according to one or more embodiments may further include additives. Examples of additives may include surfactants, crosslinking agents, leveling agents, quenchers, and / or (e.g., any suitable) combinations thereof.

[0134] Surfactants may include, for example, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts and / or (e.g., any suitable) combinations thereof, but this disclosure is not limited thereto.

[0135] The crosslinking agent may be, for example, a melamine crosslinking agent, a substituted urea crosslinking agent, an acrylic crosslinking agent, an epoxy crosslinking agent, or a polymer crosslinking agent, but this disclosure is not limited thereto. The crosslinking agent may have at least two crosslinking-forming substituents; for example, the crosslinking agent may be a compound such as methoxymethylated glycourea, butoxymethylated glycourea, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanidine, butoxymethylated benzoguanidine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, methacrylate, 1,4-butanediol diglycidyl ether, glycidol, diglycidyl 1,2-cyclohexane dicarboxylate, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, and / or similar compounds.

[0136] Leveling agents can be used to improve the flatness of coatings during printing, and suitable leveling agents can be commercially available.

[0137] The quencher may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminenaphthalene and / or (e.g., any suitable combination thereof).

[0138] The amount of these other additives can be controlled or selected depending on the desired or suitable properties.

[0139] In one or more embodiments, the semiconductor photoresist composition may further include a silane coupling agent as an adhesion enhancer to improve the tightness of contact 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 containing carbon-carbon unsaturated bonds, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane; or 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane; trimethoxy[3-(phenylamino)propyl]silane and / or the like, but this disclosure is not limited thereto.

[0140] Semiconductor photoresist compositions can be formed into patterns with a high aspect ratio without collapse (e.g., non-collapsed patterns). Therefore, to form fine patterns with widths of, for example, about 5 nanometers to about 100 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 70 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, semiconductor photoresist compositions can be used in photoresist processes using light with wavelengths ranging from about 5 nanometers to about 150 nanometers, for example, 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. Therefore, semiconductor photoresist compositions according to some example embodiments can be used to achieve extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5 nanometers.

[0141] According to some example embodiments, a method for forming a pattern using the aforementioned semiconductor photoresist composition is provided. For example, the pattern produced may be a photoresist pattern.

[0142] A method for forming a pattern according to some example embodiments includes: forming an etch target layer on a substrate, coating a semiconductor photoresist composition on the etch target layer to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and using the photoresist pattern as an etch mask to etch the etch target layer.

[0143] The following is for reference Figures 1A-1E Describes a method for forming patterns using semiconductor photoresist compositions. Figures 1A-1E This is a cross-sectional view used to explain a method of forming patterns using semiconductor photoresist compositions according to some example embodiments.

[0144] Reference Figure 1AAn object for etching is prepared. The object for etching may be a thin film 102 formed on a semiconductor substrate 100. Hereinafter, by way of example, the object for etching is limited to the thin film 102. The surface of the thin film 102 is washed to remove any remaining impurities and / or similar substances thereon. The thin film 102 may be, for example, a silicon nitride layer, a polycrystalline silicon layer, or a silicon oxide layer.

[0145] Subsequently, the resist underlayer composition for forming the resist underlayer 104 is spin-coated onto the surface of the washed film 102. However, one or more embodiments are not limited thereto, and any suitable coating method may be used, such as spraying, dip coating, knife coating, printing methods (e.g., inkjet printing and / or screen printing), and / or similar methods.

[0146] In some embodiments, the resist underlayer coating process may not be provided. Hereinafter, as an example, a process including resist underlayer coating is described.

[0147] The coated composition is then dried and baked to form a resist underlayer 104 on the film 102. Baking may be performed at about 100°C to about 500°C, for example, about 100°C to about 300°C.

[0148] The resist underlayer 104 is formed between the substrate 100 and the photoresist layer 106, and thus prevents or reduces the non-uniformity of the photoresist linewidth and the ability to form unwanted patterns when rays reflected from the interface between the substrate 100 and the photoresist layer 106 or from the hard mask between the layers are scattered into the unwanted photoresist area.

[0149] Reference Figure 1B A photoresist layer 106 is formed by coating a semiconductor photoresist composition onto a resist substrate 104. The photoresist layer 106 is obtained by coating the aforementioned semiconductor photoresist composition onto a thin film 102 formed on a substrate 100 and then curing it by heat treatment.

[0150] In some embodiments, patterning using a semiconductor photoresist composition may include applying the semiconductor photoresist composition onto a substrate 100 having a thin film 102 by spin coating, slot coating, inkjet printing and / or similar methods, and subsequently drying it to form a photoresist layer 106.

[0151] The composition of semiconductor photoresist has been described in detail and will not be described again.

[0152] Subsequently, the substrate 100 having the photoresist layer 106 is subjected to a first baking process. The first baking process may be performed at about 80°C to about 120°C.

[0153] Reference Figure 1C The photoresist layer 106 can be selectively exposed using a patterned mask 110.

[0154] For example, exposure can use activating radiation with high-energy wavelengths, such as EUV (extreme ultraviolet; wavelength about 13.5 nm), E-Beam (electron beam) and / or similar, as well as light with wavelengths such as i-line (wavelength about 365 nm), KrF excimer laser (wavelength about 248 nm), ArF excimer laser (wavelength about 193 nm) and / or similar.

[0155] According to some example embodiments, the light used for exposure may have a wavelength in the range of about 5 nanometers to about 150 nanometers or a high-energy wavelength, such as EUV (extreme ultraviolet; wavelength 13.5 nanometers), E-Beam (electron beam) and / or the like.

[0156] By utilizing cross-linking reactions (e.g., condensation between organometallic compounds) to form polymers, the exposed region 106b of the photoresist layer 106 has different solubility than the unexposed region 106a of the photoresist layer 106.

[0157] Subsequently, the substrate 100 undergoes a second baking process. The second baking process can be performed at a temperature of about 90°C to about 200°C. The exposed area 106b of the photoresist layer 106 becomes insoluble in the developer (e.g., easily insoluble) due to the second baking process.

[0158] exist Figure 1D In this process, a developer is used to dissolve and remove the unexposed areas 106a of the photoresist layer to form a photoresist pattern 108. For example, the unexposed areas 106a of the photoresist layer are dissolved and removed using an organic solvent such as 2-heptanone and / or similar substances to complete the photoresist pattern 108 corresponding to a negative image.

[0159] As described above, the developing solution used in the patterning method according to some example embodiments may be an organic solvent. The organic solvent used in the patterning method according to some example 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-propanol, 1-butanol, isopropanol, 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; and / or combinations thereof (e.g., any suitable combination).

[0160] However, the photoresist pattern according to some example embodiments is not limited to a negative image, but can be formed to have a positive image. Here, the developer used to form the positive image can be a quaternary ammonium hydroxide composition, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and / or combinations thereof (e.g., any suitable combination).

[0161] As described above, exposure to high-energy light, such as EUV (extreme ultraviolet; wavelength 13.5 nm), E-Beam (electron beam), and / or similar light, and light with wavelengths such as i-line (wavelength about 365 nm), KrF excimer laser (wavelength about 248 nm), ArF excimer laser (wavelength about 193 nm), and / or similar light, can provide a photoresist pattern 108 with a width (e.g., having a width) of about 5 nm to about 100 nm. For example, the photoresist pattern 108 may have a width (e.g., having 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.

[0162] Additionally, the photoresist pattern 108 may have a pitch, with a half-pitch less than or equal to about 50 nanometers, for example less than or equal to about 40 nanometers, less than or equal to about 30 nanometers, less than or equal to about 20 nanometers, or less than or equal to about 15 nanometers, and a linewidth 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.

[0163] Subsequently, the photoresist pattern 108 is used as an etching mask to etch the resist substrate 104. Through this etching process, an organic layer pattern 112 is formed. The organic layer pattern 112 may also have a width corresponding to the width of the photoresist pattern 108.

[0164] Reference Figure 1E The exposed thin film 102 is etched by applying a photoresist pattern 108 as an etching mask. Thus, the thin film is formed as a thin film pattern 114.

[0165] 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 mixture thereof.

[0166] In the exposure process, the thin film pattern 114 formed by the photoresist pattern 108 formed using an exposure process performed using an EUV light source can have a width corresponding to the width of the photoresist pattern 108. For example, the thin film pattern 114 can have a width of about 5 nanometers to about 100 nanometers, which is equal to or substantially equal to the width of the photoresist pattern 108. For example, the thin film pattern 114 formed by the photoresist pattern 108 formed using an exposure process performed using an EUV light source can 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, about 5 nanometers to about 20 nanometers, or less than or equal to about 20 nanometers, which is the same as or similar to the width of the photoresist pattern 108.

[0167] The present disclosure will be described in more detail below through examples of the preparation of the aforementioned semiconductor photoresist composition. However, the present disclosure is not technically limited to the following examples.

[0168] Synthesis of organometallic compounds

[0169] Synthesis Example 1

[0170] Add 40.7 g of t-butylSnPh3 and 300 g of propionic acid to a 250 mL two-necked round-bottom flask and heat under reflux for 24 hours.

[0171] Unreacted propionic acid was removed under reduced pressure to obtain the compound represented by chemical formula 6.

[0172] [Chemical Formula 6]

[0173]

[0174] Synthesis Example 2

[0175] 30 mL of anhydrous pentane was added to 10 g of t-pentylSnCl3 (t-AmylSnCl3) and the temperature was maintained at 0°C. 7.4 g of diethylamine and 6.1 g of ethanol were then added, and the mixture was stirred at room temperature for 1 hour. When the reaction was complete, the resulting product was filtered, concentrated, and vacuum dried to obtain the compound represented by chemical formula 7.

[0176] [Chemical Formula 7]

[0177]

[0178] Synthesis Example 3

[0179] 10 g of dibutyltin dichloride was dissolved in 30 mL of diethyl ether, and 70 mL of 1 M sodium hydroxide (NaOH) aqueous solution was added. The mixture was then stirred for 1 hour. After stirring, the resulting solid was filtered, washed three times with 25 mL of deionized water, and dried at 100 °C under reduced pressure to obtain an organometallic compound represented by chemical formula 8 with a weight-average molecular weight of 1,500.

[0180] [Chemical Formula 8]

[0181]

[0182] (Preparation of semiconductor photoresist composition)

[0183] Examples 1 to 13 and Comparison Examples 1 to 3

[0184] Each semiconductor photoresist composition of Examples 1 to 12 and Comparative Examples 1 to 4 was prepared by dissolving the organic acid compound (propionic acid, 0.05 wt%) and organometallic compound (2.95 wt%) represented by chemical formulas 6 to 8 of Synthetic Examples 1 to 3 at a combined concentration of 3 wt% in each of the organic solvents S1 to S5 of the compositions shown in Table 1, and then filtering the obtained solution through a 0.1-micron PTFE (polytetrafluoroethylene) syringe filter.

[0185] (Table 1)

[0186]

[0187] (S3:S4* Mixing weight ratio = 70:30)

[0188] S1: 2-Heptanone

[0189] S2: Cyclohexanone

[0190] S3: 2-Pentanone

[0191] S4: Propylene glycol methyl ether acetate (PGMEA)

[0192] S5: Methyl isobutyl carbinol (MIBC)

[0193] Assessment 1: Evaluation of Sensitivity and Line Edge Roughness (LER)

[0194] Each photoresist composition of the examples and comparative examples was spin-coated at 1500 rpm for 30 seconds on a 200 mm circular silicon wafer with HMDS deposited on its surface, baked at 110 degrees Celsius for 60 seconds (baking was performed after coating (post-coating baking, PAB)), and left to stand at room temperature (23 ± 2 degrees Celsius) for 30 seconds.

[0195] Subsequently, using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET), a linear array of 50 circular pads, each 500 micrometers in diameter, was projected onto each wafer coated with a photoresist composition. The pad exposure time was adjusted to ensure that an increased dose of EUV light was applied to each pad.

[0196] Subsequently, the resist and substrate are exposed on a hot plate at 160 degrees Celsius for 120 seconds, and then baked. The baked film is developed with PGMEA solvent to form a negative image. Finally, the resulting film is baked again on a hot plate at 150 degrees Celsius for 2 minutes to complete the process.

[0197] Critical dimension (CD)-SEM was used to measure the resist linewidth as a function of exposure dose (energy). The differences in resist linewidth formed at different exposure doses were used to confirm the appropriate or suitable sensitivity based on the exposure dose, and the sensitivity and LER were evaluated according to the following criteria. The results are shown in Table 2.

[0198] [Sensitivity Evaluation Criteria]

[0199] A: Less than 50mJ / cm 2

[0200] B: Greater than or equal to 50 mJ / cm 2

[0201] [LER Assessment Criteria]

[0202] ○: Less than or equal to 2 nanometers

[0203] △: Greater than 2 nanometers and less than or equal to 5 nanometers

[0204] X: Greater than 5 nanometers

[0205] Evaluation 2: Evaluation of latency characteristics

[0206] Each photoresist composition of the examples and comparative examples was spin-coated at 1500 rpm for 30 seconds on a 200 mm circular silicon wafer with HMDS deposited on its surface, then baked at 100 to 120 degrees Celsius (post-coating baking, PAB) for 60 seconds, and left to stand at room temperature for 10 minutes (process delay time).

[0207] Subsequently, a linear array of 50 circular pads, each 500 micrometers in diameter, was projected onto a wafer coated with a photoresist composition using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). The pad exposure time was adjusted to apply an increased EUV dose to each pad.

[0208] Subsequently, the resist and substrate are exposed on a hot plate at 180 degrees Celsius for 120 seconds, and then baked. The baked film is developed with PGMEA solvent to form a negative image, and finally baked on a hot plate at 150 degrees Celsius for 2 minutes to complete the process.

[0209] The linewidth of the resist formed by exposure with the same dose (energy) was measured using CD-SEM. The linewidth (CD) of each resist pattern formed according to the process delay time (10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes) was measured to calculate the delay characteristics according to Equation 1. The results are shown in Table 2.

[0210] [Calculation Formula 1]

[0211] Delay characteristic = {Maximum CD value among the CD values ​​of each pattern formed within 60 minutes after PAB at 10-minute intervals / CD value of the pattern formed without rest} * 100

[0212] [Evaluation Criteria]

[0213] ◎: △CD is greater than 2% and less than or equal to 7%

[0214] ○: △CD is greater than 7% and less than or equal to 15%

[0215] X: △CD is greater than 15%

[0216] (Table 2)

[0217] Sensitivity LER Delay characteristics Comparative Example 1 B ○ △ Comparative Example 2 B ○ △ Example 1 A ○ ◎ Example 2 B ○ ○ Example 3 A ○ ◎ Example 4 A ○ ◎ Comparative Example 3 B △ △ Example 5 B ○ ○ Example 6 B ○ ○ Example 7 B ○ ◎ Example 8 B ○ ◎ Comparative Example 4 B ○ △ Example 9 B ○ ○ Example 10 B ○ ○ Example 11 B ○ ○ Example 12 B ○ ◎

[0218] As can be seen from the results in Table 2, the patterns formed using the semiconductor photoresist composition according to the examples have enhanced (e.g., superior or suitable) sensitivity and / or delay characteristics compared to the patterns formed using the semiconductor photoresist composition according to the comparative examples.

[0219] For example, it should be apparent that patterns formed using the semiconductor photoresist composition according to the examples exhibit enhanced sensitivity and delay characteristics compared to patterns formed using the semiconductor photoresist composition according to the comparative examples. Specifically, the photoresist composition in the examples demonstrates superior sensitivity, as evidenced by the lower exposure dose required to achieve the desired patterning. Furthermore, the line edge roughness (LER) of patterns formed using these compositions remains consistently low, ensuring higher precision and quality in semiconductor devices. Delay characteristics evaluated based on the critical size (CD) value over time show that the photoresist composition in the examples maintains its performance stability even after extended process delays. This stability is crucial for practical applications in semiconductor manufacturing, as process delays are common. Overall, the semiconductor photoresist composition according to the examples provides significant improvements in both sensitivity and delay characteristics, making it well-suited for advanced semiconductor device fabrication.

[0220] In other words, Examples 1 through 12 detail the preparation and evaluation of semiconductor photoresist compositions using various organometallic compounds and organic solvents. These compositions were tested for sensitivity, line edge roughness (LER), and delay characteristics. Examples 1 through 4 used chemical formula 6 with different solvents (S1 through S4) and mixtures of S3 and S4. These compositions exhibited excellent sensitivity and LER, with some demonstrating superior delay characteristics. Examples 5 through 8 used chemical formula 7 with different solvents (S1 through S4) and mixtures of S3 and S4. These compositions generally exhibited good sensitivity and LER, with some showing improved delay characteristics. Examples 9 through 12 used chemical formula 8 with different solvents (S1 through S4) and mixtures of S3 and S4. These compositions consistently exhibited good sensitivity and LER, with some showing enhanced delay characteristics. Comparative Examples 1 through 4 used the same organometallic compounds as the examples but with different solvents (S4 and S5). Compared to the examples, the comparative compositions generally exhibited lower sensitivity and less desirable delay characteristics.

[0221] It will be further understood that when the terms “comprises,” “including,” “has, have, having,” “includes and / or including” are used, they may specify the presence of the stated features, integers, steps, operations, elements, and / or components, but do not exclude the presence or addition of other features, integers, steps, operations, elements, components, and / or any combination thereof. For example, it will be understood that the terms “comprise(s) / comprising,” “include(s) / including,” or “have / has / having” specify the presence of the stated features, integers, steps, operations, elements, and / or components, but do not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof. Furthermore, the terms “comprise(s) / comprising,” “include(s) / including,” “have / has / having,” or other similar terms include or support the terms “consisting of” and “consisting essentially of,” indicating the presence of the stated feature, integer, step, operation, element, and / or component, without or substantially without the presence of other features, integers, steps, operations, elements, components, and / or groups thereof.

[0222] As used herein, the term "combination thereof" refers to mixtures, laminates, complexes, copolymers, alloys, blends, reaction products and / or similar components.

[0223] As used herein, the terms “use” and “utilization” can be considered synonymous with the terms “exploitation” and “utilization”, respectively. As used herein, when expressions such as “at least one,” “one,” and “selected from” precede a list of elements, they modify the entire list of elements rather than individual elements within the list. For example, “selected from at least one of a, b, and c,” “at least one of a, b, or c,” and “at least one of a, b, and / or c” can mean only a, only b, only c, both a and b (e.g., simultaneously), both a and c (e.g., simultaneously), both b and c (e.g., simultaneously), all a, b, and c, or variations thereof.

[0224] When describing embodiments of an inventive concept, the word "may" refers to "one or more embodiments of the inventive concept".

[0225] As used herein, the term “about” and similar terms are used as approximate terms rather than terms of degree, intended to take into account the inherent biases in measured or calculated values ​​that would be recognized by one of skill in the art. As used herein, “about” includes the value and means within an acceptable range of deviation for a particular value as determined by one of skill in the art, taking into account the relevant measurement and errors associated with the measurement of the particular quantity (i.e., limitations of the measurement system). For example, “about” may mean within one or more standard deviations, or within ±30%, 20%, 10%, or 5% of the value.

[0226] Furthermore, any numerical range described herein is intended to include all subranges within the described range that are of the same numerical precision. For example, the range “1.0 to 10.0” is intended to include all subranges between (and including) the described minimum value of 1.0 and the described maximum value of 10.0, i.e., a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as 2.4 to 7.6. Any maximum numerical limit described herein is intended to include all lower numerical limits contained therein, and any minimum numerical limit described in this specification is intended to include all higher numerical limits contained therein. Therefore, the applicant reserves the right to amend this specification (including the claims) to expressly describe any subranges that are included within the range expressly described herein.

[0227] Those skilled in the art will understand that, based on the entirety of this disclosure, each suitable feature of the various embodiments of this disclosure may be combined with each other or partially or completely combined with other features, and may be technically combined and operated with each other in various suitable ways, and each embodiment may be implemented independently or in any suitable manner in cooperation with each other, unless otherwise stated or implied.

[0228] According to the embodiments described herein, the patterning apparatus, or any other related device / apparatus or component, can be implemented using any suitable hardware, firmware (e.g., application-specific integrated circuit), software, or a combination of software, firmware, and hardware. For example, various components of the apparatus can be formed on an integrated circuit (IC) chip or on a separate IC chip. Furthermore, various components of the apparatus can be implemented on a flexible printed circuit film, a tape-on-a-carrier package (TCP), a printed circuit board (PCB), or formed on a substrate. Additionally, various components of the apparatus can be processes or threads running on one or more processors, executing calculator program instructions and interacting with other system components in one or more computing devices to perform the various functions described herein. Calculator program instructions are stored in memory, which can be implemented in the computing device using standard memory devices, such as random access memory (RAM). Calculator program instructions can also be stored on other non-transitory calculator-readable media, such as CD-ROMs, flash drives, or the like. Furthermore, those skilled in the art will recognize that the functions of various computing devices can be combined or integrated into a single computing device, or the functions of a particular computing device can be distributed across one or more other computing devices without departing from the scope of the embodiments disclosed herein.

[0229] In the foregoing, certain embodiments have been described and illustrated. However, it will be apparent to those skilled in the art that this disclosure is not limited to one or more embodiments as described, and that various modifications and transformations can be made without departing from the spirit and scope of this disclosure. Therefore, these modified or transformed embodiments should not be understood separately from the technical concept and aspects of this disclosure, and the modified embodiments are within the scope of the claims and their equivalents.

Claims

1. A semiconductor photoresist composition, comprising: an organometallic compound; an organic solvent including a ketone solvent; and an organic acid compound. 2.The semiconductor photoresist composition of claim 1, wherein the ketone solvent is represented by Chemical Formula 1 or Chemical Formula 2: [Chemical Formula 1] in Chemical Formula 1, wherein [Chemical Formula 2] R 1 and R 2 each independently is substituted or unsubstituted C1to C10alkyl; wherein, in Chemical Formula 2, and Ring A is a substituted or unsubstituted C3 to C10 cycloalkyl. 3.The semiconductor photoresist composition of claim 2, wherein the ketone solvent represented by Chemical Formula 1 is represented by any one selected from Chemical Formula 1-1 to Chemical Formula 1-4: in Chemical Formula 1-1 to Chemical Formula 1-4, and wherein, n1 is an integer of 1 to 7, R 1a is substituted or unsubstituted methyl, R 1b is substituted or unsubstituted ethyl, R 1c is substituted or unsubstituted propyl, R 1d is substituted or unsubstituted butyl, R 3 is substituted or unsubstituted methyl, n2 is an integer of 1 to 6, n3 is an integer of 1 to 5, n4 is an integer of 1 to 4, and 4.The semiconductor photoresist composition of claim 3, wherein R 4 and R 5 each independently is hydrogen, halogen, substituted or unsubstituted C1to C5alkyl, substituted or unsubstituted C3to C10cycloalkyl, substituted or unsubstituted C6to C12aryl, or a combination thereof. n1 is an integer of 1 to 5, n2 is an integer of 1 to 4, n3 is an integer of 1 to 3, and n4 is 1 or 2. 5.The semiconductor photoresist composition of claim 3, wherein the ketone solvent represented by Chemical Formula 1 is represented by any one of Chemical Formula 1-1 to Chemical Formula 1-3, n1 is an integer of 1 to 3, n2 is 1 or 2, and n3 is 1. 6.The semiconductor photoresist composition of claim 3, wherein the ketone solvent represented by Chemical Formula 1 is represented by Chemical Formula 1-1 or Chemical Formula 1-2, n1 is 1 or 2, and n2 is 1. 7.The semiconductor photoresist composition of claim 1, wherein the organic solvent including the ketone solvent further includes an acetate solvent. 8.The semiconductor photoresist composition of claim 7, wherein a weight ratio between the ketone solvent and the acetate solvent is 99:1 to 50:

50. 9.The semiconductor photoresist composition of claim 1, wherein a boiling point of the organic solvent including the ketone solvent is 100 to 160℃. 10.The semiconductor photoresist composition of claim 1, wherein an amount of the organic solvent including the ketone solvent is 70wt% to 99.5wt% based on 100wt% of the semiconductor photoresist composition. 11.The semiconductor photoresist composition of claim 1, wherein an amount of the organometallic compound is 0.5wt% to 30wt% based on 100wt% of the semiconductor photoresist composition. 12.The semiconductor photoresist composition of claim 1, wherein the organic acid compound is selected from toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, fluorinated sulfonate, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, and combinations thereof. 13.The semiconductor photoresist composition of claim 1, wherein the semiconductor photoresist composition further includes an additive selected from a surfactant, a crosslinking agent, a leveling agent, a quencher, and combinations thereof. 14.The semiconductor photoresist composition of claim 1, wherein ​ The organic metal compound is an organotin compound including an organic oxy group and / or an organic carbonyloxy group.

15. The semiconductor photoresist composition of claim 1, wherein The organic metal compound is represented by Chemical Formula 3: [Chemical Formula 3] wherein In Chemical Formula 3, R 6 substituted or unsubstituted C1to C20alkyl, substituted or unsubstituted C3to C20cycloalkyl, substituted or unsubstituted C2to C20alkenyl, substituted or unsubstituted C2to C20alkynyl, substituted or unsubstituted C6to C30aryl, and substituted or unsubstituted C7to C30aralkyl, R 7 to R 9 each independently substituted or unsubstituted C3 to C20 cycloalkyl; substituted or unsubstituted C2 to C20 alkenyl; substituted or unsubstituted C2 to C20 alkynyl; substituted or unsubstituted C6 to C30 aryl; substituted or unsubstituted C7 to C30 aralkyl; alkoxy or aryloxy represented by -OR b , wherein R b is substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof; carboxyl represented by -O(CO)R c , wherein R c is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof; alkylamide or dialkylamide group represented by -NR d R e , wherein R d and R e each independently are hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof; amido represented by -NR f (COR g ), wherein R f and R g each independently are hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof; amido represented by -NR h C(NR i )R j , wherein R h , R i and R j each independently are hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof; sulfido represented by -SR k alkylthio or arylthiol group represented by R-S-, wherein R k is a substituted or unsubstituted Ci to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof; or a thiocarboxyl group represented by -S(CO)R l , wherein R l is hydrogen, a substituted or unsubstituted Ci to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof; and R 7 R 9 R b R c R d R e R f R g R h R i R j R k R l R 16. The semiconductor photoresist composition of claim 15, wherein R 7 at least one of R 9 is alkoxy or aryloxy represented by -OR b or carboxy represented by -O(CO)R c .

17. The semiconductor photoresist composition of claim 16, wherein R 6 substituted or unsubstituted C1to C8alkyl, substituted or unsubstituted C3to C8cycloalkyl, substituted or unsubstituted C2to C8aliphatic unsaturated organic radical comprising one or more double or triple bonds, substituted or unsubstituted C6to C20aryl, substituted or unsubstituted C4to C20heteroaryl, carbonyl, ethoxy, propoxy, or a combination thereof, R b substituted or unsubstituted C1to C8alkyl, substituted or unsubstituted C3to C8cycloalkyl, substituted or unsubstituted C2to C8alkenyl, substituted or unsubstituted C2to C8alkynyl, substituted or unsubstituted C6to C20aryl, or a combination thereof, and R c is hydrogen, substituted or unsubstituted C1to C8alkyl, substituted or unsubstituted C3to C8cycloalkyl, substituted or unsubstituted C2to C8alkenyl, substituted or unsubstituted C2to C8alkynyl, substituted or unsubstituted C6to C20aryl, or a combination thereof.

18. The semiconductor photoresist composition of claim 1, wherein The organic metal compound is represented by Chemical Formula 4 or Chemical Formula 5: [Chemical Formula 4] R 10 z SnO (2-(z / 2)-(x / 2)) (OH) x , wherein In Chemical Formula 4, R 10 is a C1to C31hydrocarbyl group, 0 < z < 2, and 0 < (z+x) < 4; [Chemical Formula 5] R 11 a Sn b X c Y d , and wherein, in Chemical Formula 5, R 11 substituted or unsubstituted C1to C20alkyl, substituted or unsubstituted C3to C20cycloalkyl, substituted or unsubstituted C2to C20aliphatic unsaturated organic group comprising one or more double or triple bonds, substituted or unsubstituted C6to C30aryl, substituted or unsubstituted C4to C30heteroaryl, carbonyl, oxiranyl, oxetanyl, or a combination thereof, X is sulfur, selenium, or tellurium, Y is -OR m or -OC(=O)R n , R m substituted or unsubstituted C1to C20alkyl, substituted or unsubstituted C3to C20cycloalkyl, substituted or unsubstituted C2to C20alkenyl, substituted or unsubstituted C2to C20alkynyl, substituted or unsubstituted C6to C30aryl, or a combination thereof, R n is hydrogen, a substituted or unsubstituted Ci to C20alkyl, a substituted or unsubstituted C3to C20cycloalkyl, a substituted or unsubstituted C2to C20alkenyl, a substituted or unsubstituted C2to C20alkynyl, a substituted or unsubstituted C6to C30aryl, or a combination thereof, and a, b, c, and d are each independently an integer of 1 to 20.

19. A method comprising: forming an etching target layer on a substrate; applying the semiconductor photoresist composition according to any one of claims 1 to 18 on the etching target layer to form a photoresist layer; patternizing the photoresist layer to form a photoresist pattern; and etching the etching target layer using the photoresist pattern as an etching mask, wherein the method is used to form a pattern.

20. The method of claim 19, wherein the patternizing of the photoresist layer includes selectively exposing the photoresist layer to a light source selected from extreme ultraviolet light, electron beam, i-line, KrF excimer laser, and ArF excimer laser.

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