Semiconductor photoresist composition and method for forming pattern using same

Abstract

Disclosed are a semiconductor photoresist composition and a method of forming a pattern using the same, the semiconductor photoresist composition comprising: an organometallic compound; an alcohol compound including an unsaturated bond; and a solvent. The present application can provide a photoresist pattern having improved sensitivity and line edge roughness characteristics.

Description

[0001] Cross-reference of related applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2024-0152904, filed on October 31, 2024, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Embodiments of this disclosure relate to a semiconductor photoresist composition and a method of patterning using the same. Background Technology

[0004] Extreme ultraviolet (EUV) lithography has attracted attention as a 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. According to EUV lithography, extremely fine patterns (e.g., less than or equal to 20 nanometers) can be formed during the exposure process in the manufacturing of semiconductor devices.

[0005] Extreme ultraviolet (EUV) lithography is achieved through the development of compatible photoresists with a spatial resolution of less than or equal to 16 nanometers. Currently, efforts are underway to meet the insufficient specifications of conventional chemically amplified (CA) photoresists for next-generation devices, such as resolution, photospeed, and feature roughness (also known as line edge roughness or LER).

[0006] The inherent image blurring caused by acid-catalyzed reactions in these polymeric photoresists limits the resolution of small feature sizes, a problem long present in electron beam lithography. Chemically amplified (CA) photoresists are designed to achieve high sensitivity, but their elemental composition reduces absorbance at 13.5 nm wavelength, thus decreasing sensitivity, which may present additional challenges for EUV exposure.

[0007] CA photoresist presents challenges at small feature sizes due to roughness issues, and experiments have shown that the line edge roughness (LER) of CA photoresist increases with decreasing photosensitivity, partly due to the nature of the acid catalyst process. Therefore, due to these defects and problems with CA photoresist, the use of high-performance photoresists is desired or necessary in the semiconductor industry.

[0008] To overcome the aforementioned drawbacks of chemically amplified (CA) organic photosensitive compositions, inorganic photosensitive compositions have been investigated. These inorganic compositions are primarily used for negative tone patterning, which exhibits resistance to removal by developer compositions due to chemical modification achieved through a non-chemical amplification mechanism. The inorganic compositions contain inorganic elements with higher EUV absorbance than hydrocarbons, thus ensuring sensitivity through a non-chemical amplification mechanism. They are also less sensitive to stochastic effects and therefore exhibit low line edge roughness and fewer defects.

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

[0010] These materials are effective for patterning large pitches in bilayer configurations, similar to far-ultraviolet (deep UV), X-ray, and electron beam sources. Recently, impressive performance has been achieved when cationic hafnium sulfate (HfSOx) materials, combined with peroxide complexing agents, are used for imaging 15 nm half-pitch (HP) chromatic lithography via projection EUV exposure (e.g., when cationic hafnium sulfate materials, combined with peroxide complexing agents, are used for imaging 15 nm half-pitch (HP) chromatic lithography via projection EUV exposure). This system exhibits the highest performance among non-CA photoresists and has a practical photosensitivity close to that suitable for EUV photoresists. However, hafnium sulfate materials with peroxide complexing agents have some practical drawbacks. First, these materials are coated with a mixture of corrosive sulfuric acid / hydrogen peroxide and exhibit insufficient stability over their shelf life. Second, as a composite mixture, it is not easy to modify its structure to achieve performance improvements. Third, development must be carried out in a solution of extremely high concentrations, such as 25 wt% tetramethylammonium hydroxide (TMAH).

[0011] Recently, tin-containing molecules with excellent extreme ultraviolet (EUV) absorption properties have been actively studied. Among these, organotin polymers, alkyl ligands are dissociated through light absorption and / or the resulting secondary electrons, and crosslink with adjacent chains via oxo bonds, thus enabling negative patterning that cannot be removed by organic developers. These organotin polymers exhibit significantly improved sensitivity while maintaining resolution and line edge roughness; however, further improvements to the patterning properties are needed for commercial viability. Summary of the Invention

[0012] Some exemplary embodiments of this disclosure provide a semiconductor photoresist composition with improved sensitivity and LER characteristics.

[0013] Some exemplary embodiments provide a method for forming patterns using a semiconductor photoresist composition.

[0014] The semiconductor photoresist composition according to some exemplary embodiments comprises: an organometallic compound; an alcohol compound including unsaturated bonds; and a solvent.

[0015] A method for forming a pattern according to some exemplary embodiments includes: providing or forming an etch target layer on a substrate; coating the etch target layer with a semiconductor photoresist composition to form a photoresist film; patterning the photoresist film to form a photoresist pattern; and using the photoresist pattern as an etch mask to etch the etch target layer.

[0016] Semiconductor photoresist compositions according to some exemplary embodiments can provide photoresist patterns with improved sensitivity and LER characteristics. Attached Figure Description

[0017] The accompanying drawings, together with the description, illustrate embodiments of the subject matter of this disclosure and, together with the description, serve to explain the principles of the embodiments of the subject matter of this disclosure.

[0018] Figures 1A to 1E This is a cross-sectional view illustrating a method of forming a pattern using a semiconductor photoresist composition according to some exemplary embodiments.

[0019] Explanation of icon numbers

[0020] 100: Substrate / Semiconductor Substrate

[0021] 102: Film

[0022] 104: Resist underlayer

[0023] 106: Photoresist film

[0024] 106a: Unexposed area

[0025] 106b: Exposure Zone

[0026] 108: Photoresist pattern

[0027] 110: Patterned mask

[0028] 112: Organic membrane pattern

[0029] 114: Thin Film Pattern Detailed Implementation

[0030] In the following description, embodiments are described in more detail with reference to the accompanying drawings. In this description of the present disclosure, well-known functions or structures will not be repeated in order to clarify the subject matter of the disclosure.

[0031] To clearly illustrate the subject matter of this disclosure, certain descriptions and relationships have been omitted, and throughout this disclosure, identical or similar configuration elements are indicated by the same reference numerals. Furthermore, since the size and thickness of each configuration shown in the accompanying drawings may be arbitrarily depicted for better understanding and ease of explanation, this disclosure is not necessarily limited thereto.

[0032] In the drawings, for clarity, the thickness of components such as layers, films, panels, and areas may be exaggerated. In the drawings, for ease of explanation, the thickness of a portion of a layer or area may be exaggerated. It will be understood that when an element (e.g., a layer, film, area, or substrate) is referred to as being "on" another element (e.g., when an element (e.g., a layer, film, area, or substrate) is referred to as being "on" another element), the element may be directly on the other element, or there may be intermediate elements present.

[0033] As used herein, the term "substituted" refers to hydrogen atoms replaced by: deuterium, halogen, hydroxyl, carboxyl, thiol, cyano, nitro, -NRR' (where R and R' are each independently 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), -SiRR'R'' (where R, R' and R' are substituted for hydrogen, ... R'' can be, independently, hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, a C1 to C30 alkyl group, a C1 to C10 haloalkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a C1 to C20 sulfide group, or a combination thereof. The term "unsubstituted" means that the hydrogen atom has not been replaced by another substituent and remains unchanged as a hydrogen atom.

[0034] Unless otherwise defined (e.g., when no other definition is provided), the term "alkyl" as used herein refers to a straight-chain or branched aliphatic hydrocarbon group. An alkyl group may be a "saturated alkyl" without any double or triple bonds.

[0035] 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.

[0036] Unless otherwise defined (e.g., when no other definition is provided), the term "cycloalkyl" as used herein refers to a monovalent cyclic aliphatic hydrocarbon group.

[0037] The cycloalkyl group can be C3 to C8 cycloalkyl, such as C3 to C7 cycloalkyl or C3 to C6 cycloalkyl. For example, the cycloalkyl group can be cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, but is not limited thereto.

[0038] As used herein, the term "aryl" refers to a substituent in which all atoms in a cyclic substituent have p orbitals and these p orbitals are conjugated, and may include monocyclic or fused-ring polycyclic functional groups (e.g., rings sharing adjacent carbon atom pairs).

[0039] The term "unsaturated bond" as used in this article refers to a double or triple bond, and there is no particular limitation on the number of unsaturated bonds in a molecule. For example, it can be ethylene, propylene, butene, pentene, hexene, and / or acetylene.

[0040] In the following text, semiconductor photoresist compositions according to some exemplary embodiments are described.

[0041] The semiconductor photoresist composition according to some exemplary embodiments comprises an organometallic compound, an alcohol compound including unsaturated bonds, and a solvent.

[0042] By incorporating an alcohol compound comprising unsaturated bonds in the semiconductor photoresist composition according to embodiments of the present disclosure, the overall composition not only promotes intermolecular bonding after exposure, but also improves sensitivity by making the resulting intermolecular bonding smoother through heat treatment after exposure.

[0043] In the embodiments, the non-shared electron pairs of the alcohol increase adsorption onto the substrate, which improves surface roughness and LER properties.

[0044] For example, an alcohol compound containing unsaturated bonds can be represented by any of the formulas 1 to 4.

[0045] [Chemical Formula 1]

[0046]

[0047] [Chemical Formula 2]

[0048]

[0049] [Chemical Formula 3]

[0050]

[0051] [Chemical Formula 4]

[0052]

[0053] In chemical formulas 1 to 4

[0054] R1 To R 12 Each of the following is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C1 to C20 alkylene, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, or a combination thereof.

[0055] L 1 and L 2 Each of these can be independently a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkyne group, or a combination thereof.

[0056] m1 to m12 are each an independent integer of 0 or 1.

[0057] m1+m2+m3+m4 and m5+m6+m7+m8 are each an independent integer from 1 to 4, and

[0058] m9+m10 and m11+m12 are each an independent integer of 1 or 2.

[0059] For example, alcohol compounds that include unsaturated bonds may include 1 to 4 -OH groups, such as 1 to 3 -OH groups, or for example 1 or 2 -OH groups.

[0060] In some exemplary embodiments, m1+m2+m3+m4 and m5+m6+m7+m8 can each be an integer from 1 to 3, such as an integer of 1 or 2.

[0061] For example, if R 1 To R 12 It is a terminal substituent (e.g., when R...) 1 To R 12 When it is a terminal substituent, it can be a substituted or unsubstituted C1 to C20 alkyl group.

[0062] For example, if R 1 To R 12 Linked to -OH groups (e.g., when R...) 1 To R 12 When attached to an -OH group, it can be a substituted or unsubstituted C1 to C20 alkylene group.

[0063] For example, if R 1 To R 12 It is a terminal substituent (e.g., when R...) 1 To R 12 When it is a terminal substituent, it can be a substituted or unsubstituted C1 to C10 alkyl group.

[0064] For example, if R 1 To R 12 Linked to -OH groups (e.g., when R...) 1 To R 12 When attached to an -OH group, it can be a substituted or unsubstituted C1 to C10 alkylene group.

[0065] For example, if R 1 To R 12 It is a terminal substituent (e.g., when R...) 1 To R 12 When it is a terminal substituent, it can be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, or a substituted or unsubstituted butyl group.

[0066] For example, if R 1 To R 12 Linked to -OH groups (e.g., when R...) 1 To R 12 When attached to an -OH group, it can be a substituted or unsubstituted methylene, a substituted or unsubstituted ethylene, a substituted or unsubstituted propylene, or a substituted or unsubstituted butylene.

[0067] For example, L 1 and L 2 Each can be an independently substituted or unsubstituted C1 to C5 alkylene group.

[0068] For example, L 1 and L 2 Each can be independently a substituted or unsubstituted methylene, a substituted or unsubstituted ethylene, or a substituted or unsubstituted propylene.

[0069] For example, alcohol compounds that include unsaturated bonds can be selected from the compounds listed in Group 1.

[0070] [Group 1]

[0071] .

[0072] Based on 100% by weight of the semiconductor photoresist composition, it may contain an alcohol compound comprising unsaturated bonds in an amount from about 0.001% by weight to about 5% by weight.

[0073] For example, based on 100% by weight of a semiconductor photoresist composition, an amount of alcohol compound comprising unsaturated bonds may be included in the composition in amounts from about 0.005% by weight to about 5% by weight, from about 0.01% by weight to about 5% by weight, or from about 0.03% by weight to about 5% by weight.

[0074] Based on 100% by weight of the semiconductor photoresist composition, an organometallic compound may be included in an amount from about 0.5% by weight to about 30% by weight.

[0075] Semiconductor photoresist compositions according to some exemplary embodiments can improve the sensitivity of the photoresist by including alcohol compounds comprising unsaturated bonds within the above-described amount range.

[0076] Organometallic compounds may be organotin compounds, including at least one selected from organooxy groups and organocarbonyl groups.

[0077] For example, organometallic compounds can be represented by chemical formula 5.

[0078] [Chemical Formula 5]

[0079]

[0080] In chemical formula 5,

[0081] R 13 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.

[0082] R 14 To R 16 Each of these can be independently 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 substituted or unsubstituted C7 to C30 aralkyl.

[0083] Alkyl and / or aryloxy (-OR) b , where R b (substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, or combinations thereof).

[0084] Carboxyl group (-O(CO)R) c , where R c (which 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, or combinations thereof).

[0085] -NR d R e , where R d and R e Each of the following is independently hydrogen, 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, or a combination thereof.

[0086] -NR f (COR g ), where R f and R g Each of the following is independently hydrogen, 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, or a combination thereof.

[0087] -NR h C(NR i )R j , where R h R i and R j Each of the following is independently hydrogen, 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, or a combination thereof.

[0088] -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, or a combination thereof.

[0089] -S(CO)R l , where R l It is hydrogen, 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, or a combination thereof, and

[0090] R 14 To R 16 At least one of them is selected from: alkoxy and / or aryloxy (-OR) b , where Rb It can be a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof), or a carboxyl group (-O(CO)R). c , where R c (which 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, or combinations thereof), -NR d R e , where R d and R e Each of the following is independently hydrogen, 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, or a combination thereof, -NR f (COR g ), where R f and R g Each of the following is independently hydrogen, 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, or a combination thereof, -NR g C(NR h )R i , where R h R i and R j Each of the following is independently hydrogen, 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, or a combination thereof, -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, or a combination thereof, and / or -S(CO)R. l R lIt 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.

[0091] R 14 To R 16 At least one of them may be selected from: alkoxy and / or aryloxy (-OR) b ) and / or carboxyl groups (-O(CO)R c ) and / or carboxyl groups (-O(CO)R c .

[0092] In the embodiments, the compounds represented by chemical formula 5 include OR b or -OC(=O)R c As a ligand, patterns formed using semiconductor photoresist compositions containing the compound can therefore exhibit excellent confinement resolution (e.g., excellent line resolution).

[0093] In the embodiment, ligand-OR b or -OC(=O)R c The solubility of the compound represented by chemical formula 5 in the solvent can be determined.

[0094] R 13 It can 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 organic group 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, or a combination thereof.

[0095] R b It may be a substituted or unsubstituted C1 to C8 alkyl, a substituted or unsubstituted C3 to C8 cycloalkyl, a substituted or unsubstituted C2 to C8 alkenyl, a substituted or unsubstituted C2 to C8 alkynyl, a substituted or unsubstituted C6 to C20 aryl, or a combination thereof, and

[0096] R c It may be hydrogen, substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 alkenyl, substituted or unsubstituted C2 to C8 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.

[0097] R 13It 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, valerate, ethoxy, propoxy, or combinations thereof.

[0098] R b It 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 combinations thereof, and

[0099] R c It 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 combinations thereof.

[0100] In the embodiments, the organometallic compound may be represented by chemical formula 6 or chemical formula 7.

[0101] [Chemical Formula 6]

[0102] R 17 z SnO (2-(z / 2)-(x / 2)) (OH) x

[0103] In chemical formula 6,

[0104] R 17 For C1 to C31 hydrocarbon groups, 0 < z ≤ 2, and 0 < (z+x) ≤ 4;

[0105] [Chemical Formula 7]

[0106] R 18 a Sn b X c Y d

[0107] In chemical formula 7,

[0108] R 18The group includes substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C3 to C20 cycloalkyl groups, substituted or unsubstituted C2 to C20 aliphatic unsaturated organic groups including one or more double or triple bonds, substituted or unsubstituted C6 to C30 aryl groups, substituted or unsubstituted C4 to C30 heteroaryl groups, carbonyl groups, ethylene oxide groups, propylene oxide groups, or combinations thereof.

[0109] X is sulfur (S), selenium (Se), or tellurium (Te).

[0110] Y is -OR m or -OC(=O)R n ,

[0111] Where R m It is 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, or a combination thereof, and

[0112] R n It is hydrogen, 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, or a combination thereof, and

[0113] a, b, c, and d are each independent integers from 1 to 20.

[0114] The solvent included in the semiconductor photoresist composition according to some exemplary embodiments may be an organic solvent, and may be, for example, an aromatic compound (e.g., xylene, toluene, etc.), an alcohol (e.g., 4-methyl-2-pentenol, 4-methyl-2-propanol, 1-butanol, methanol, isopropanol, 1-propanol, etc.), an ether (e.g., anisole, tetrahydrofuran, etc.), an ester (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, etc.), a ketone (e.g., methyl ethyl ketone, 2-heptanone, etc.) or a mixture thereof, but is not limited thereto.

[0115] In addition to the organometallic compounds, alcohol compounds including unsaturated bonds, and solvents described above, the semiconductor photoresist compositions according to some exemplary embodiments may also contain resins.

[0116] The resin may be a phenolic resin comprising at least one of the aromatic moieties listed in Group 2.

[0117] [Group 2]

[0118]

[0119] The resin may have a weight-average molecular weight of about 500 to about 20,000.

[0120] 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.

[0121] If the resin is included in the above-mentioned amount range, it can have excellent etch resistance and heat resistance.

[0122] In the embodiments, the semiconductor photoresist composition may be composed of the above-mentioned organometallic compound, alcohol compound including unsaturated bonds, solvent and resin.

[0123] The semiconductor photoresist composition according to the above embodiments may also include additives as needed. Examples of additives may be surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0124] Surfactants may include, for example, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts, or combinations thereof, but are not limited thereto.

[0125] The crosslinking agent may be, for example, a melamine crosslinking agent, a substituted urea crosslinking agent, an acrylic crosslinking agent, an epoxy resin crosslinking agent, and / or a polymer crosslinking agent, but is not limited thereto. For example, the crosslinking agent may be a crosslinking agent having at least two crosslinking-forming substituents, such as methoxymethylated glycourea, butoxymethylated glycourea, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, propylene methacrylate, 1,4-butanediol diglycidyl ether, glycidyl, 1,2-cyclohexanedicarboxylic acid diglycidyl ether, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, etc.

[0126] Leveling agents can be used to improve the flatness of coatings during printing and can be any suitable leveling agent commonly used in the art.

[0127] Organic acids may include, but are not limited to, p-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, or combinations thereof.

[0128] The quencher may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0129] The amount of each additive can be controlled according to its appropriate or required properties.

[0130] In embodiments, the semiconductor photoresist composition may further comprise 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 comprising carbon-carbon unsaturated bonds, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane; and / or 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane; trimethoxy[3-(phenylamino)propyl]silane, etc., but is not limited thereto.

[0131] Semiconductor photoresist compositions can be formed into patterns with a high aspect ratio and no (or substantially no) collapse. Therefore, in order 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 in the wavelength range of 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 exemplary embodiments can be used to achieve extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5 nanometers.

[0132] According to some exemplary embodiments, a method for forming a pattern using the above-described semiconductor photoresist composition is provided. For example, the pattern produced may be a photoresist pattern.

[0133] A method for forming a pattern according to some exemplary embodiments includes: providing or forming an etch target layer on a substrate, coating a semiconductor photoresist composition on the etch target layer to form a photoresist film, patterning the photoresist film to form a photoresist pattern, and using the photoresist pattern as an etch mask to etch the etch target layer.

[0134] In the following text, refer to Figures 1A to 1E This paper describes a method for forming patterns using semiconductor photoresist compositions. Figures 1A to 1E This is a cross-sectional view illustrating a method of forming a pattern using a semiconductor photoresist composition according to some exemplary embodiments.

[0135] Reference Figure 1A The object to be etched is prepared. The object to be etched may be a thin film 102 formed on a semiconductor substrate 100. In the following, the object to be etched is limited to the thin film 102, but the present disclosure is not limited thereto. The surface of the thin film 102 is washed to remove impurities and 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.

[0136] Subsequently, the resist underlayer composition used to form the resist underlayer 104 is spin-coated onto the surface of the washed film 102. However, the embodiments are not limited to this, and various suitable coating methods can be used, such as spraying, dip coating, doctor blade coating, printing methods (e.g., inkjet printing and screen printing), etc.

[0137] The coating process of the resist underlayer can be omitted, and the process including the coating of the resist underlayer is described below.

[0138] 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.

[0139] The resist underlayer 104 is located between the substrate 100 and the photoresist film 106, and therefore can prevent or reduce non-uniformity of photoresist linewidth and patterning if rays reflected from the interface between the substrate 100 and the photoresist film 106 and / or from the hard mask between the layers are scattered into unintended photoresist areas (e.g., when rays reflected from the interface between the substrate 100 and the photoresist film 106 and / or from the hard mask between the layers are scattered into unintended photoresist areas).

[0140] Reference Figure 1B A photoresist film 106 is formed by coating a semiconductor photoresist composition onto a resist substrate 104. The photoresist film 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.

[0141] In an embodiment, patterning using a semiconductor photoresist composition may include coating the semiconductor photoresist composition onto a substrate 100 having a thin film 102 by spin coating, slot coating, inkjet printing, etc., and then drying it to form a photoresist film 106.

[0142] Semiconductor photoresist compositions have been described in detail in this document and will not be repeated here.

[0143] Subsequently, the substrate 100 having the photoresist film 106 is subjected to a first baking process. The first baking process may be performed at approximately 80°C to approximately 120°C.

[0144] Reference Figure 1C The photoresist film 106 can be selectively exposed using a patterned mask 110.

[0145] For example, exposure can use activation radiation that utilizes the following types of light: high-energy wavelengths such as extreme ultraviolet (EUV; wavelength approximately 13.5 nm) and electron beam (E-Beam); and shorter wavelengths such as i-line (wavelength approximately 365 nm), KrF excimer laser (wavelength approximately 248 nm), and ArF excimer laser (wavelength approximately 193 nm).

[0146] In the embodiments, the light used for exposure, according to some exemplary embodiments, may be light with a wavelength in the range of about 5 nanometers to about 150 nanometers, and high-energy wavelengths, such as extreme ultraviolet (EUV; wavelength of 13.5 nanometers), electron beam (E-Beam), etc.

[0147] Because polymers are formed through cross-linking reactions between organometallic compounds, such as condensation (e.g., condensation reaction), the exposed area 106b of the photoresist film 106 has a different solubility than the unexposed area 106a of the photoresist film 106.

[0148] Subsequently, the substrate 100 is subjected to a second baking process. The second baking process can be performed at a temperature of about 90°C to about 200°C. Due to the second baking process, the exposure area 106b of the photoresist film 106 becomes less soluble relative to the developer.

[0149] exist Figure 1D In this process, a developer is used to dissolve and remove the unexposed areas 106a of the photoresist film to form a photoresist pattern 108. For example, an organic solvent such as 2-heptanone is used to dissolve and remove the unexposed areas 106a of the photoresist film to complete the photoresist pattern 108 corresponding to a negative image.

[0150] As described above, the developer used in the pattern forming method according to some exemplary embodiments may be an organic solvent. The organic solvent used in the pattern forming method according to some exemplary embodiments may be, for example: ketones, such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, etc.; alcohols, such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, methanol, etc.; esters, such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, etc.; aromatic compounds, such as benzene, xylene, toluene, etc.; or combinations thereof.

[0151] However, the photoresist pattern according to some exemplary embodiments is not limited to a negative image, but can be formed to have a positive image. In the embodiments, the developer used to form the positive image can be a quaternary ammonium hydroxide composition, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or a combination thereof.

[0152] As described above, exposure to high-energy light, such as extreme ultraviolet (EUV; wavelength 13.5 nm) or electron beam (E-Beam), and shorter wavelength light, such as i-line (wavelength approximately 365 nm), KrF excimer laser (wavelength approximately 248 nm), or ArF excimer laser (wavelength approximately 193 nm), can provide a photoresist pattern 108 with a width of approximately 5 nm to approximately 100 nm. For example, the photoresist pattern 108 may have a width of approximately 5 nm to approximately 90 nm, approximately 5 nm to approximately 80 nm, approximately 5 nm to approximately 70 nm, approximately 5 nm to approximately 60 nm, approximately 5 nm to approximately 50 nm, approximately 5 nm to approximately 40 nm, approximately 5 nm to approximately 30 nm, or approximately 5 nm to approximately 20 nm.

[0153] In an embodiment, the photoresist pattern 108 may have a pitch of less than or equal to about 50 nanometers, for example less than or equal to about 40 nanometers, for example less than or equal to about 30 nanometers, for example less than or equal to about 20 nanometers, or for example less than or equal to about 15 nanometers, and a linewidth roughness of 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.

[0154] Subsequently, the photoresist pattern 108 is used as an etching mask to etch the resist substrate 104. Through this etching process, an organic film pattern 112 is formed. The organic film pattern 112 may also have a width corresponding to the width of the photoresist pattern 108.

[0155] Reference Figure 1E The exposed thin film 102 is etched by using a photoresist pattern 108 as an etching mask. Thus, the thin film is formed into a thin film pattern 114.

[0156] 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 and / or a mixture thereof.

[0157] In the exposure process, the thin film pattern 114 formed using the photoresist pattern 108 can have a width corresponding to the width of the photoresist pattern 108, which is formed by an exposure process using an EUV light source. For example, the thin film pattern 114 can have a width of about 5 nanometers to about 100 nanometers, which is equal to the width of the photoresist pattern 108. For example, like the width of the photoresist pattern 108, the thin film pattern 114 formed using the photoresist pattern 108 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, or about 5 nanometers to about 20 nanometers, or for example, a width less than or equal to about 20 nanometers, which is formed by an exposure process using an EUV light source.

[0158] The embodiments of this disclosure are described in more detail below with reference to examples of preparing the above-described semiconductor photoresist compositions. However, this disclosure is not technically limited to the following examples.

[0159] Synthesis of organometallic compounds

[0160] Synthesis example 1

[0161] 40.7 g of tert-butylSnPh3 and 300 g of propionic acid were added to a 250 ml double-necked round-bottom flask and refluxed for 24 hours.

[0162] Unreacted propionic acid was removed under reduced pressure, thus yielding the compound represented by chemical formula 8.

[0163] [Chemical Formula 8]

[0164]

[0165] Synthesis example 2

[0166] 30 ml of anhydrous pentane was added to 10 g of tert-amyl SnCl3, the temperature was maintained at 0 °C, and then 7.4 g of diethylamine and 6.1 g of ethanol were added, and the mixture was stirred at room temperature for 1 hour. When the reaction was complete, the product was filtered, concentrated, and vacuum dried to obtain the compound represented by chemical formula 9.

[0167] [Chemical Formula 9]

[0168]

[0169] Synthesis example 3

[0170] 10 g of dichlorodibutyltin was dissolved in 30 mL of 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 under reduced pressure at 100 °C to obtain an organometallic compound represented by formula 10 with a weight-average molecular weight of 1,500.

[0171] [Chemical Formula 10]

[0172]

[0173] Preparation of semiconductor photoresist compositions

[0174] Examples 1 to 13 and Comparative Examples 1 to 3

[0175] The organometallic compounds obtained in Synthesis Examples 1 to 3 were each dissolved in 3% propylene glycol methyl ether acetate (PGMEA), and alcohol compounds C1 to C5 were added to dissolve them at the concentrations listed in Table 1. The solutions were then filtered through a 0.1-micron polytetrafluoroethylene (PTFE) syringe filter to prepare each semiconductor photoresist composition according to the examples and comparative examples. Each composition was coated onto a silicon wafer to a thickness of 240 Å, and then patterned films were fabricated using PAB, exposure, PEB, and development processes.

[0176] [Table 1]

[0177]

[0178]

[0179] Assessment 1: Evaluation of surface roughness (Rq)

[0180] Each photoresist composition was spin-coated onto a wafer at 1500 rpm for 60 seconds and baked at 110°C for 60 seconds to form a thin film. Images of the thin films were captured using an atomic force microscope (AFM) or similar instrument, and the images were used to measure the surface roughness of the thin films using software (e.g., an optical profilometer) according to the following reference. The results are shown in Table 2.

[0181] Evaluation criteria for surface roughness (Rq value)

[0182] - ○: Less than or equal to 0.4

[0183] - △: Greater than 0.4 and less than or equal to 0.7

[0184] - X: greater than 0.7

[0185] Evaluation 2: Evaluation of Sensitivity and LER Characteristics

[0186] Each of the photoresist compositions according to the examples and comparative examples was spin-coated at 1500 rpm onto a 200 mm circular silicon wafer for 30 seconds, the surface of which was deposited with hexamethyldisilazane (HMDS), and then baked at 110°C for 60 seconds. After application, baking (post-application baking, PAB) was performed, and then the wafer was left at room temperature (23 ± 2°C) for 30 seconds.

[0187] Then, a 50-nanometer-wide line array is projected onto a wafer coated with a photoresist composition using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). Here, the pad exposure time is adjusted to ensure that an increased dose of EUV light is applied to each pad.

[0188] Then, after exposure, the photoresist and substrate are baked on a hot plate at 160°C for 120 seconds. The baked film is then developed in PGMEA solvent to form a negative image. Finally, the resulting film is baked again on a hot plate at 150°C for 2 minutes to complete the process.

[0189] The change in resist linewidth as a function of exposure dose (energy) was measured using a critical dimension scanning electron microscope (CD-SEM). The sensitivity to exposure dose was confirmed by the different resist linewidth values ​​formed according to various exposure doses, and the sensitivity and LER were evaluated according to the following criteria, and the results are shown in Table 2.

[0190] Sensitivity evaluation criteria

[0191] - A: Less than 16 mJ / cm 2

[0192] - B: Greater than or equal to 16 mJ / cm 2 And less than 18 mJ / cm 2

[0193] - C: Greater than or equal to 18 mJ / cm 2 And less than 20 mJ / cm2

[0194] - D: Greater than or equal to 20 mJ / cm 2

[0195] LER evaluation criteria

[0196] - ◎: ​​Less than 2 nanometers

[0197] - ○: Greater than or equal to 2 nanometers and less than 4 nanometers

[0198] - △: Greater than or equal to 4 nanometers and less than 6 nanometers

[0199] - X: 6 nanometers or greater

[0200] [Table 2]

[0201]

[0202] According to the results in Table 2, the semiconductor photoresist compositions of Examples 1 to 13 exhibit superior sensitivity and LER characteristics compared to Comparative Examples 1 to 3.

[0203] In the foregoing, exemplary embodiments have been described and illustrated. However, it will be apparent to those skilled in the art that this disclosure is not limited to the described embodiments, and various modifications and variations can be suitably made without departing from the spirit and scope of this disclosure. Therefore, the modified or varied embodiments are not to be understood separately from the technical concept and aspects of this disclosure, and the modified embodiments are within the scope of the claims of this disclosure and their equivalents.

Claims

1. A semiconductor photoresist composition comprising: Organometallic compounds; Alcohols containing unsaturated bonds; and Solvent.

2. The semiconductor photoresist composition according to claim 1, wherein: The alcohol compound containing the aforementioned unsaturated bond is represented by any one of chemical formulas 1 to 4: [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] Among chemical formulas 1 to 4, R 1 To R 12 Each of the following is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C1 to C20 alkylene, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, or a combination thereof. L 1 and L 2 Each of these can be independently a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkyne group, or a combination thereof. m1 to m12 are each an independent integer of 0 or 1. m1+m2+m3+m4 and m5+m6+m7+m8 are each an independent integer from 1 to 4, and m9+m10 and m11+m12 are each an independent integer of 1 or 2.

3. The semiconductor photoresist composition according to claim 1, wherein: m1+m2+m3+m4 and m5+m6+m7+m8 are each an independent integer of 1 or 2.

4. The semiconductor photoresist composition according to claim 1, wherein: The alcoholic compound containing the aforementioned unsaturated bond is selected from one of the compounds listed in Group 1: [Group 1] 。 5. The semiconductor photoresist composition according to claim 1, wherein: The semiconductor photoresist composition comprises, in an amount from 0.001% to 5% by weight, the alcohol compound containing the unsaturated bonds.

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

7. The semiconductor photoresist composition according to claim 1, wherein: The semiconductor photoresist composition further comprises surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof as additives.

8. The semiconductor photoresist composition according to claim 1, wherein: The organometallic compound contains at least one selected from organooxy groups and organocarbonyl groups.

9. The semiconductor photoresist composition according to claim 1, wherein: The organometallic compound is represented by chemical formula 5: [Chemical Formula 5] In chemical formula 5, R 13 It is 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. R 14 To R 16 Each of the following is independently 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, -OR b -O(CO)R c -NR d R e -NR f (COR g -NR h C(NR i )R j -SR k or -S(CO)R l , 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 C6 to C30 aryl, or a combination thereof. Where R c It 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. Where R d and R e Each of the following is independently hydrogen, 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, or a combination thereof. Where R f and R g Each of the following is independently hydrogen, 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, or a combination thereof. Where R h R i and R j Each of the following is independently hydrogen, 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, or a combination thereof. 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, or a combination thereof. Where R l It 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. R 14 To R 16 At least one of them is selected from -OR b -O(CO)R c -NR d R e -NR f (COR g -NR h C(NR i )R j -SR k or -S(CO)R l .

10. The semiconductor photoresist composition according to claim 9, wherein: R 14 To R 16 At least one of them is selected from -OR b or -O(CO)R c .

11. The semiconductor photoresist composition according to claim 10, wherein: R 13 The substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 aliphatic unsaturated organic groups including one or more double or triple bonds, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C4 to C20 heteroaryl, carbonyl, ethoxy, propoxy, or combinations thereof, R b It is a substituted or unsubstituted C1 to C8 alkyl, a substituted or unsubstituted C3 to C8 cycloalkyl, a substituted or unsubstituted C2 to C8 alkenyl, a substituted or unsubstituted C2 to C8 alkynyl, a substituted or unsubstituted C6 to C20 aryl, or a combination thereof, and R c It is hydrogen, substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 alkenyl, substituted or unsubstituted C2 to C8 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.

12. The semiconductor photoresist composition according to claim 1, wherein: The organometallic compound is represented by chemical formula 6 or chemical formula 7: [Chemical Formula 6] R 17 z SnO (2-(z / 2)-(x / 2)) (OH) x In chemical formula 6, R 17 For C1 to C31 hydrocarbon groups, 0 < z ≤ 2, and 0 < (z+x) ≤ 4; [Chemical Formula 7] R 18 a Sn b X c Y d In chemical formula 7, R 18 The substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C3 to C20 cycloalkyl groups, substituted or unsubstituted C2 to C20 aliphatic unsaturated organic groups including one or more double or triple bonds, substituted or unsubstituted C6 to C30 aryl groups, substituted or unsubstituted C4 to C30 heteroaryl groups, carbonyl groups, ethylene oxide groups, propylene oxide groups, or combinations thereof. X represents sulfur, selenium, or tellurium. Y is -OR m or -OC(=O)R n , Where R m It is 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, or a combination thereof, and R n It is hydrogen, 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, or a combination thereof, and a, b, c, and d are each independent integers from 1 to 20.

13. A method for forming a pattern, comprising: Provide an etching target layer on the substrate; The semiconductor photoresist composition as described in any one of claims 1 to 12 is coated onto the etched target layer to form a photoresist film; The photoresist film is patterned to form a photoresist pattern; as well as The photoresist pattern is used as an etching mask to etch the target layer.

Images