Semiconductor photoresist composition and method of forming patterns using the same

Abstract

To provide a semiconductor photoresist composition that can achieve excellent sensitivity and excellent LER characteristics.SOLUTION: The present invention relates to a semiconductor photoresist composition including: a Sn-containing organometallic compound; a carboxylic acid compound; at least one compound selected from sulfonic acid compounds and phosphonic acid compounds; and a solvent, and a method of forming patterns using the semiconductor photoresist composition.SELECTED DRAWING: Figure 5

Description

Technical Field

[0001] This description relates to a composition for a semiconductor photoresist and a pattern forming method using the same.

Background Art

[0002] As one of the elemental technologies for manufacturing next-generation semiconductor devices, EUV (extreme ultraviolet light) lithography has attracted attention. EUV lithography is a pattern forming technology that uses EUV light with a wavelength of 13.5 nm as an exposure light source. According to EUV lithography, it has been demonstrated that extremely fine patterns (for example, 20 nm or less) can be formed in the exposure process of the semiconductor device manufacturing process.

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

[0004] The intrinsic image blur caused by acid catalyzed reactions in these polymeric photoresists limits resolution at small feature sizes, a fact long known in e-beam lithography. Chemically amplified (CA) photoresists are designed for high sensitivity, but their typical elemental makeup reduces the absorbance of the photoresist at a wavelength of 13.5 nm, and as a result, they may experience additional difficulties under EUV exposure, in part because it reduces sensitivity.

[0005] CA photoresists also experience difficulties due to roughness issues at small feature sizes, and it has been experimentally shown that as the photospeed decreases, the line edge roughness (LER) increases, partly due to the nature of the acid catalysis process. Due to the drawbacks and problems of CA photoresists, there is a need in the semiconductor industry for new types of high-performance photoresists.

[0006] To overcome the shortcomings of the chemically amplified organic photosensitive compositions described above, inorganic photosensitive compositions have been studied. In the case of inorganic photosensitive compositions, they are mainly used for negative tone patterning that is resistant to removal by a developer composition through chemical modification by a non-chemically amplified mechanism. In the case of inorganic compositions, they contain inorganic elements with a higher EUV absorption rate compared to hydrocarbons, and it is known that sensitivity can be ensured even with a non-chemically amplified mechanism, they are less sensitive to the stochastic effect, and the number of line edge roughnesses and defects is also small.

[0007] Inorganic photoresists based on peroxopolyacids of tungsten and tungsten mixed with niobium, titanium, and / or tantalum have been reported for use as radiation sensitive materials for patterning (US5061599,; H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298 - 300, 1986).

[0008] These materials are deep UV, x-ray, and electron beam sources that have been effective in patterning large features in bilayer configurations. More recently, cationic hafnium metal oxide sulfate (HfSOx) materials with peroxo complexing agents have shown impressive performance when used to image a 15 nm half-pitch (HP) by projection EUV lithography (US2011-0045406; J.K. Stowers, A. Telecky, M. Kocsis, B.L. Clark, D.A. Keszler, A. Grenville, C.N. Anderson, P.P. Naulleau, Proc. SPIE, 7969, 796915, 2011). This system shows top performance for non-CA photoresists and has a photospeed approaching the requirements for a viable EUV photoresist. However, hafnium metal oxide sulfate materials with peroxo complexing agents have several practical drawbacks. First, these materials are coated with a highly corrosive sulfuric acid / hydrogen peroxide mixture and do not have good shelf-life stability. Second, structural modifications for performance improvement are not easy as a complex mixture. Third, they must be developed with very high concentration solutions such as 25 wt% tetramethylammonium hydroxide (TMAH).

[0009] Recently, with the discovery that tin-containing molecules exhibit excellent extreme ultraviolet absorption, intensive research has been conducted. In the case of organotin polymers, for example, negative-tone patterning that cannot be removed by an organic developer solution due to crosslinking via oxo bonds with peripheral chains while alkyl ligands dissociate by light absorption or secondary electrons generated thereby is possible. Such organotin polymers have shown a dramatic improvement in sensitivity while maintaining resolution and line edge roughness. However, for commercialization, further improvement of the patterning characteristics is required.

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] One embodiment provides a composition for a semiconductor photoresist that is excellent in sensitivity and line edge roughness (LER) characteristics and has improved sensitivity.

[0011] Another embodiment provides a patterning method using the composition for a semiconductor photoresist.

MEANS FOR SOLVING THE PROBLEMS

[0012] A composition for a semiconductor photoresist according to one embodiment includes a Sn-containing organometallic compound; a carboxylic acid compound; at least one of a sulfonic acid compound and a phosphonic acid compound; and a solvent.

[0013] A patterning method according to another embodiment includes forming an etching target film on a substrate; applying the composition for a semiconductor photoresist described above on the etching target film to form a photoresist film; patterning the photoresist film to form a photoresist pattern; and etching the etching target film using the photoresist pattern as an etching mask.

EFFECTS OF THE INVENTION

[0014] The semiconductor photoresist composition according to one embodiment enables the realization of excellent sensitivity and excellent LER characteristics.

Brief Description of the Drawings

[0015]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Embodiments for Carrying Out the Invention

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

[0017] In order to clearly explain this description, parts that are unnecessary for explanation are omitted, and the same reference numerals are assigned to the same or similar components throughout the specification. Also, the sizes and thicknesses of each configuration shown in the drawings are arbitrarily shown for convenience of explanation, so this description is not necessarily limited to the illustration.

[0018] For clarity in the drawings, the thicknesses have been exaggerated to show the various layers and regions. Also, in the drawings, for the sake of convenience in explanation, the thicknesses of some layers and regions have been exaggerated. When a part such as a layer, film, region, or plate is said to be "on" another part, this includes not only the case where it is directly "above" the other part, but also the case where there are other parts in between.

[0019] In this description, "substituted" means that a hydrogen atom is replaced by deuterium, a halogen group, a hydroxy group, a carboxyl group, a thiol group, a cyano group, a nitro group, -NRR' (where R and R' are each independently hydrogen, a substituted or unsubstituted C1 - C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 - C30 saturated or unsaturated cycloaliphatic hydrocarbon group, or a substituted or unsubstituted C6 - C30 aromatic hydrocarbon group), -SiRR'R" (where R, R', and R" are each independently hydrogen, a substituted or unsubstituted C1 - C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 - C30 saturated or unsaturated cycloaliphatic hydrocarbon group, or a substituted or unsubstituted C6 - C30 aromatic hydrocarbon group), a C1 - C30 alkyl group, a C1 - C10 haloalkyl group, a C1 - C10 alkylsilyl group, a C3 - C30 cycloalkyl group, a C6 - C30 aryl group, a C1 - C20 alkoxy group, a C1 - C20 sulfide group, or a combination thereof. "Unsubstituted" means that the hydrogen atom remains as a hydrogen atom without being replaced by another substituent.

[0020] In this specification, unless otherwise defined, the term "alkyl group" means a straight-chain or branched-chain aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0021] The alkyl group may be a C1-C8 alkyl group. For example, the alkyl group may be a C1-C7 alkyl group, a C1-C6 alkyl group, or a C1-C5 alkyl group. For example, the C1-C5 alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group, or a 2,2-dimethylpropyl group.

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

[0023] The cycloalkyl group may be a C3-C8 cycloalkyl group, for example, a C3-C7 cycloalkyl group, a C3-C6 cycloalkyl group, a C3-C5 cycloalkyl group, or a C3-C4 cycloalkyl group. For example, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and is not limited thereto.

[0024] In this specification, the "aliphatic unsaturated organic group" means a hydrocarbon group in which the bond between carbon atoms in the molecule contains a double bond, a triple bond, or a combination of these bonds.

[0025] The aliphatic unsaturated organic group may be a C2-C8 aliphatic unsaturated organic group. For example, the aliphatic unsaturated organic group may be a C2-C7 aliphatic unsaturated organic group, a C2-C6 aliphatic unsaturated organic group, a C2-C5 aliphatic unsaturated organic group, or a C2-C4 aliphatic unsaturated organic group. For example, the C2-C4 aliphatic unsaturated organic group may be a vinyl group, an ethynyl group, an allyl group, a 1-propenyl group, a 1-methyl-1-propenyl group, a 2-propenyl group, a 2-methyl-2-propenyl group, a 1-propynyl group, a 1-methyl-1-propynyl group, a 2-propynyl group, a 2-methyl-2-propynyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group.

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

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

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

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

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

[0031] A composition for a semiconductor photoresist according to an embodiment of the present invention may include at least one of a Sn-containing organometallic compound, a carboxylic acid compound, a sulfonic acid compound, and a phosphonic acid compound, and a solvent.

[0032] The composition for the semiconductor photoresist contains at least two kinds of acid compounds, that is, together with a carboxylic acid compound, at least one of a sulfonic acid compound and a phosphonic acid compound, whereby the sensitivity and LER are improved and excellent resolution can be achieved.

[0033] As an example, the carboxylic acid compound: at least one of the sulfonic acid compound and the phosphonic acid compound is contained in a weight ratio of 1:0.001 to 1:10.

[0034] As a specific example, the carboxylic acid compound: at least one of the sulfonic acid compound and the phosphonic acid compound is contained in a weight ratio of 1:0.01 to 1:7.

[0035] The carboxylic acid compound is represented by the following Chemical Formula 1. [Chemical Formula] In the Chemical Formula 1, R 1 is an amine group, a halogen, a hydroxy group, a carboxyl group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C7-C30 arylalkyl group, L 1 and L 2 are each independently a single bond, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C6-C30 arylene group, or a combination thereof, X 1 is a single bond, O, S or NR 2 (R 2is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), and m1 is an integer of 1 or more.

[0036] The upper limit value of m1 may be the maximum value connectable to L 2 but m1 may be within a range not exceeding the maximum value, for example, in the range of 1 to 10, 1 to 8, 1 to 6, or 1 to 3.

[0037] The sulfonic acid compound is represented by the following Chemical Formula 2.

Chemical Formula

[0038] The upper limit value of m2 may be the maximum value connectable to L, but m2 may be within the range below the maximum value, for example, in the range of 1 to 10, 1 to 8, 1 to 6, or 1 to 3. 4 The upper limit value of m2 may be the maximum value connectable to L, but m2 may be within the range below the maximum value, for example, in the range of 1 to 10, 1 to 8, 1 to 6, or 1 to 3.

[0039] The phosphonic acid compound is represented by the following Chemical Formula 3. [Chemical Formula] In Chemical Formula 3, R 5 is an amine group, halogen, hydroxy group, carboxyl group, substituted or unsubstituted C1 - C20 alkyl group, substituted or unsubstituted C3 - C20 cycloalkyl group, substituted or unsubstituted C2 - C20 alkenyl group, substituted or unsubstituted C2 - C20 alkynyl group, substituted or unsubstituted C6 - C30 aryl group, or substituted or unsubstituted C7 - C30 arylalkyl group, L 5 and L 6 are each independently a single bond, substituted or unsubstituted C1 - C20 alkylene group, substituted or unsubstituted C6 - C30 arylene group, or a combination thereof, X 3 is a single bond, O, S or NR 6 (R 6 is hydrogen, substituted or unsubstituted C1 - C20 alkyl group, substituted or unsubstituted C3 - C20 cycloalkyl group, substituted or unsubstituted C2 - C20 alkenyl group, substituted or unsubstituted C2 - C20 alkynyl group, substituted or unsubstituted C6 - C30 aryl group, or a combination thereof), m3 is an integer of 1 or more.

[0040] The upper limit value of m3 may be the maximum value connectable to L, but m3 may be within the range below the maximum value, for example, in the range of 1 to 10, 1 to 8, 1 to 6, or 1 to 3. 6 The upper limit value of m3 may be the maximum value connectable to L, but m3 may be within the range below the maximum value, for example, in the range of 1 to 10, 1 to 8, 1 to 6, or 1 to 3.

[0041] For example, the above R1 , R 3 and R 5 may each independently be a hydroxy group, a carboxyl group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted iso-propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted iso-butyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted benzyl group.

[0042] For example, the aforementioned L 1 ~L 6 may each independently be a single bond, a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, a substituted or unsubstituted pentylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group.

[0043] As a specific example, the carboxylic acid compound may be one of the compounds listed in Group 1 below. [Chemical formula]

[0044] As a specific example, the sulfonic acid compound and the phosphonic acid compound may be one of the compounds listed in Group 2 below. [Chemical formula]

[0045] The carboxylic acid compound and at least one of the sulfonic acid compound and the phosphonic acid compound are contained in a total amount of 0.001 to 10% by weight based on 100% by weight of the composition for semiconductor photoresist.

[0046] For example, the carboxylic acid compound and at least one of the sulfonic acid compound and the phosphonic acid compound are contained in a total amount of 0.01 to 10% by weight, 0.01 to 5% by weight, 0.05 to 5% by weight, or 0.1 to 5% by weight based on 100% by weight of the semiconductor photoresist composition.

[0047] The Sn-containing organometallic compound is contained in an amount of 0.5% by weight to 30% by weight based on 100% by weight of the semiconductor photoresist composition.

[0048] By the semiconductor photoresist composition according to one embodiment containing the Sn-containing organometallic compound, the carboxylic acid compound, and at least one of the sulfonic acid compound and the phosphonic acid compound within the above content ranges, the sensitivity of the photoresist can be improved.

[0049] The semiconductor photoresist composition according to one embodiment can contain the Sn-containing organometallic compound: the carboxylic acid compound and at least one of the sulfonic acid compound and the phosphonic acid compound in a weight ratio of 99:1 to 80:20. For example, the semiconductor photoresist composition can contain the Sn-containing organometallic compound: the carboxylic acid compound and at least one of the sulfonic acid compound and the phosphonic acid compound in a weight ratio of 99:1 to 90:10.

[0050] When the weight ratio of the Sn-containing organometallic compound and the acid compound satisfies the above range, a semiconductor photoresist composition having excellent sensitivity can be provided.

[0051] The Sn-containing organometallic compound can contain at least one of an organic oxy group and an organic carbonyloxy group.

[0052] The organometallic compound is represented by the following Chemical Formula 4.

Chemical formula

[0053] Said R 8 ~R 10 at least one of is alkoxo and aryloxo (-OR a , where R a is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), and carboxyl group (-O(CO)R b , R b is selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof).

[0054] On the one hand, the compound represented by the chemical formula 4 contains -OR a or -OC(=O)R b By including this, the pattern formed using the composition for a semiconductor photoresist containing this can exhibit excellent resolution limit.

[0055] Also, the ligand of -OR a or -OC(=O)R b can determine the solubility of the compound represented by the chemical formula 4 in a solvent.

[0056] Said R 7 is a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C4-C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof, R a is a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof, R b may be hydrogen, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

[0057] Said R 7is a methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylyl group, benzyl group, formyl group, acetyl group, propanoyl group, butanoyl group, pentanoyl group, ethoxy group, propoxy group, or a combination thereof, R a is an ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylyl group, benzyl group, or a combination thereof, R b is hydrogen, an ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylyl group, benzyl group, or a combination thereof.

[0058] In addition, the Sn-containing organometallic compound is represented by the following Chemical Formula 5 or Chemical Formula 6. [Chemical Formula] In the Chemical Formula 5, R 11 is a C1-C31 hydrocarbyl group, where 0 < z ≦ 2 and 0 < (z + x) ≦ 4; [Chemical Formula] In the Chemical Formula 6, R 12is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C4-C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof, X is sulfur (S), selenium (Se) or tellurium (Te), Y is -OR l or -OC(=O)R m wherein, said R l is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof, R m is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof, Said a1, b1, c1 and d1 are each independently an integer from 1 to 20.

[0059] The solvent contained in the semiconductor photoresist composition according to an embodiment may be an organic solvent. As an example, it may include aromatic compounds (e.g., xylene, toluene), alcohols (e.g., 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropyl alcohol, 1-propanol), ethers (e.g., anisole, tetrahydrofuran), esters (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate), ketones (e.g., methyl ethyl ketone, 2-heptanone), mixtures thereof, etc., but is not limited thereto.

[0060] In addition to the Sn-containing organometallic compound, acid compound, and solvent, the semiconductor resist composition according to an embodiment may further contain a resin.

[0061] The resin may be a phenolic resin containing at least one aromatic moiety listed in Group 3 below.

Chemical formula

[0062] The resin is contained in an amount of 0.1% by weight to 50% by weight based on the total content of the semiconductor photoresist composition.

[0063] When the resin is contained within the above content range, it can have excellent etching resistance and heat resistance.

[0064] On the other hand, the semiconductor photoresist composition preferably consists of the aforementioned Sn-containing organometallic compound, acid compound, solvent, and resin.

[0065] The semiconductor photoresist composition according to the foregoing embodiments may further contain an additive in some cases. Examples of the additive include a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, or a combination thereof.

[0066] As the surfactant, for example, an alkylbenzene sulfonate, an alkylpyridinium salt, polyethylene glycol, a quaternary ammonium salt, or a combination thereof can be used, but it is not limited thereto.

[0067] Examples of the crosslinking agent include a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, an acrylic-based crosslinking agent, an epoxy-based crosslinking agent, or a polymer-based crosslinking agent, etc., but it is not limited thereto. As the crosslinking agent having at least two crosslinking-forming substituents, for example, compounds such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, acrylic methacrylate, 1,4-butanediol diglycidyl ether, glycidol, diglycidyl 1,2-cyclohexanedicarboxylate, trimethylolpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea can be used.

[0068] The leveling agent is for improving the coating flatness during printing, and a known leveling agent available by a commercial method can be used.

[0069] The organic acid may be, but is not limited to, 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, or a combination thereof.

[0070] The inhibitor may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0071] The usage amounts of these additives can be easily adjusted according to the desired physical properties and may be omitted.

[0072] In addition, for the semiconductor photoresist composition, in order to improve the adhesion to the substrate (for example, to improve the adhesion between the semiconductor photoresist composition and the substrate), a silane coupling agent can be further used as an additive as an adhesion promoter. The silane coupling agent can be, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; carbon-carbon unsaturated bond-containing silane compounds such as trimethoxy[3-(phenylamino)propyl]silane, etc., but is not limited thereto.

[0073] The composition for semiconductor photoresist does not cause pattern collapse even when forming a pattern having a high aspect ratio. Therefore, for example, for forming a fine pattern having a width of 5 nm to 100 nm, for example, a fine pattern having a width of 5 nm to 80 nm, for example, a fine pattern having a width of 5 nm to 70 nm, for example, a fine pattern having a width of 5 nm to 50 nm, for example, a fine pattern having a width of 5 nm to 40 nm, for example, a fine pattern having a width of 5 nm to 30 nm, for example, a fine pattern having a width of 5 nm to 20 nm, it can be used in a photoresist process using light with a wavelength of 5 nm to 150 nm, for example, a photoresist process using light with a wavelength of 5 nm to 100 nm, for example, a photoresist process using light with a wavelength of 5 nm to 80 nm, for example, a photoresist process using light with a wavelength of 5 nm to 50 nm, for example, a photoresist process using light with a wavelength of 5 nm to 30 nm, for example, a photoresist process using light with a wavelength of 5 nm to 20 nm. Therefore, when using the composition for semiconductor photoresist according to one embodiment, extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5 nm can be realized.

[0074] On the other hand, according to another embodiment, a method of forming a pattern using the above-described composition for semiconductor photoresist can be provided. As an example, the manufactured pattern may be a photoresist pattern.

[0075] The pattern formation method according to one embodiment includes the steps of forming an etching target film on a substrate, applying the above-described composition for semiconductor photoresist on the etching target film to form a photoresist film, patterning the photoresist film to form a photoresist pattern, and etching the etching target film using the photoresist pattern as an etching mask.

[0076] Hereinafter, a method for forming a pattern using the above-described composition for a semiconductor photoresist will be described with reference to FIGS. 1 to 5. FIGS. 1 to 5 are cross-sectional views for explaining a method for forming a pattern using the composition for a semiconductor photoresist according to the present invention.

[0077] Referring to FIG. 1, first, an object to be etched is provided. As an example of the object to be etched, it may be a thin film 102 formed on a semiconductor substrate 100. Hereinafter, the description will be made only in the case where the object to be etched is the thin film 102. To remove contaminants and the like remaining on the thin film 102, the surface of the thin film 102 is cleaned. The thin film 102 may be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film.

[0078] Next, a composition for forming a resist underlayer film for forming a resist underlayer film 104 is coated on the surface of the cleaned thin film 102 by applying a spin coating method. However, one embodiment is not necessarily limited thereto, and various known coating methods, for example, spray coating, dip coating, knife edge coating, printing methods, such as inkjet printing and screen printing, may be used.

[0079] The coating process of the resist underlayer film can be omitted, and hereinafter, the case of coating the resist underlayer film will be described.

[0080] Thereafter, drying and baking steps are performed to form a resist underlayer film 104 on the thin film 102. The baking treatment is performed at about 100 to about 500 ° C., and can be performed, for example, at about 100 ° C. to about 300 ° C.

[0081] The resist underlayer film 104 is formed between the substrate 100 and the photoresist film 106, and can prevent the non-uniformity of the photoresist linewidth and the pattern formability from being hindered when the irradiation rays reflected from the interface between the substrate 100 and the photoresist film 106 or the interlayer hardmask are scattered into an unintended photoresist region.

[0082] Referring to FIG. 2, the above-described semiconductor photoresist composition is coated on the resist underlayer film 104 to form a photoresist film 106. The photoresist film 106 may be in a form cured by a heat treatment process after the above-described semiconductor photoresist composition is coated on the thin film 102 formed on the substrate 100.

[0083] More specifically, the step of forming a pattern using the semiconductor photoresist composition may include a step of applying the above-described semiconductor photoresist composition on the substrate 100 on which the thin film 102 is formed by spin coating, slit coating, inkjet printing, etc., and a step of drying the applied semiconductor photoresist composition to form a photoresist film 106.

[0084] Since the semiconductor photoresist composition has already been described in detail, redundant description is omitted.

[0085] Next, a first baking step of heating the substrate 100 on which the photoresist film 106 is formed is performed. The first baking step can be performed at a temperature of about 80°C to about 120°C.

[0086] Referring to FIG. 3, the photoresist film 106 is selectively exposed using the patterned mask 110.

[0087] As an example, examples of light that can be used in the exposure process include not only light having a short wavelength such as activation irradiation line i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), but also light having a high energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm), E-Beam (electron beam), and the like.

[0088] More specifically, the exposure light according to one embodiment may be short-wavelength light having a wavelength range of 5 nm to 150 nm, or may be light having a high energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm), E-Beam (electron beam), and the like.

[0089] The exposed region 106a in the photoresist film 106 has a different solubility from the unexposed region 106b of the photoresist film 106 by forming a polymer by a crosslinking reaction such as condensation between organometallic compounds.

[0090] Next, a second baking process is performed on the substrate 100. The second baking process can be performed at a temperature of about 90°C to about 200°C. By performing the second baking process, the exposed region 106a of the photoresist film 106 becomes a state in which it is difficult to dissolve in the developer.

[0091] FIG. 4 shows a photoresist pattern 108 formed by dissolving and removing the photoresist film 106b corresponding to the unexposed region using a developer. Specifically, after dissolving the photoresist film 106b corresponding to the unexposed region using an organic solvent such as 2-heptanone and then removing it, the photoresist pattern 108 corresponding to the negative tone image is completed.

[0092] As described above, the developer used in the pattern formation method according to an embodiment may be an organic solvent. Examples of the organic solvent used in the pattern formation method according to an embodiment include ketones such as methyl ethyl ketone, acetone, cyclohexanone, and 2-heptanone; alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, and methanol; esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, and butyrolactone; aromatic compounds such as benzene, xylene, and toluene; or combinations thereof.

[0093] However, the photoresist pattern according to an embodiment is not necessarily limited to the formation of a negative-tone image, and may be formed to have a positive-tone image. In this case, examples of the developer that can be used for positive-tone image formation include quaternary ammonium hydroxide compositions such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof.

[0094] As described above, the photoresist pattern 108 formed by exposure with light having a wavelength such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), etc., or light having high energy such as EUV (Extreme UltraViolet; wavelength 13.5 nm), E-Beam (electron beam), etc., can have a thickness width of 5 nm to 100 nm. As an example, the photoresist pattern 108 is formed to have a thickness width of 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, or 5 nm to 20 nm.

[0095] On the one hand, the photoresist pattern 108 can have a half-pitch of about 50 nm or less, for example, 40 nm or less, for example, 30 nm or less, for example, 20 nm or less, for example, 15 nm or less, and a pitch with a line width roughness of about 10 nm or less, about 5 nm or less, about 3 nm or less, about 2 nm or less.

[0096] Next, the resist underlayer film 104 is etched using the photoresist pattern 108 as an etching mask. In such an etching process, an organic film pattern 112 is formed. The formed organic film pattern 112 can also have a width corresponding to the photoresist pattern 108.

[0097] Referring to FIG. 5, the thin film 102 exposed by applying the photoresist pattern 108 as an etching mask is etched. As a result, the thin film is formed into a thin film pattern 114.

[0098] The etching of the thin film 102 can be performed, for example, by dry etching using an etching gas, and the etching gas can be, for example, CHF3, CF4, Cl2, BCl3, and a mixed gas thereof.

[0099] In the exposure process performed earlier, the thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process using an EUV light source can have a width corresponding to the photoresist pattern 108. As an example, it can have the same width as the photoresist pattern 108, which is 5 nm to 100 nm. For example, the thin film pattern 114 formed by the exposure process using an EUV light source can have a width of 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, 5 nm to 20 nm, similar to the photoresist pattern 108, and more specifically, it may be formed with a width of 20 nm or less.

Example

[0100] Hereinafter, the present invention will be described in more detail through examples related to the production of the above-described composition for semiconductor photoresist. However, the technical features of the present invention are not limited by the following examples.

[0101] Synthesis of Organometallic Compounds Synthesis Example 1 Place 40.7 g of t-butylSnPh3 and 300 g of propionic acid in a 250 ml two-necked round-bottom flask, and heat under reflux for 24 hours.

[0102] Remove unreacted propionic acid under reduced pressure to obtain a compound represented by the following Chemical Formula 7.

Chemical Formula

[0103] Synthesis Example 2 Dissolve 18.9 g of iPrSn(NEt2)3 in 500 mL of anhydrous hexane in a 1 L round-bottom flask. After cooling the flask to -78°C, slowly add 9.0 g of iPrOH dropwise, and then react at room temperature for 24 hours. After the reaction is completed, concentrate and then dry under vacuum to obtain a compound represented by the following Chemical Formula 8.

Chemical Formula

[0104] Synthesis Example 3 Dissolve 10 g of dibutyltin dichloride in 30 mL of ether, then add 70 mL of 1 M aqueous sodium hydroxide (NaOH) solution, and stir for 1 hour. After stirring, filter the generated solid, wash it three times with 25 mL of deionized water, and then perform drying under reduced pressure at 100°C to obtain an organometallic compound having a weight average molecular weight of 1,500 represented by the following Chemical Formula 9.

Chemical Formula

[0105] Production of Composition for Semiconductor Photoresist Examples 1 to 9 and Comparative Examples 1 to 3 The organometallic compounds represented by Chemical Formulas 7 to 9 obtained in Synthesis Examples 1 to 3, a carboxylic acid compound, and a phosphonic acid compound were dissolved in Propylene glycol methyl ether acetate (PGMEA) at a concentration of 3 wt% at the weight ratios shown in Table 1 below, and filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to produce a composition for a semiconductor photoresist.

[0106] [Table 1]

[0107] C1: Propionic acid P1: 3-Phosphonopropanoic acid S1: 3-Hydroxypropane-1-sulfonic acid

[0108] Evaluation 1: Sensitivity and Line Edge Roughness (LER) evaluation On a 200 mm circular silicon wafer whose surface was vapor-deposited with HMDS, the photoresist compositions according to the above Examples and Comparative Examples were each spin-coated at 1500 rpm for 30 seconds, baked at 110 °C for 60 seconds (post-apply bake, PAB), and then left at room temperature (23 ± 2 °C) for 30 seconds.

[0109] Thereafter, 50 circular pad linear arrays with a diameter of 500 μm were projected onto the wafer coated with the photoresist composition using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). The pad exposure time was adjusted so that the EUV increased dose was applied to each pad.

[0110] Thereafter, the resist and the substrate were exposed on a hot plate at 160 °C for 120 seconds and then baked. The baked film was developed with a PGMEA solvent to form a negative tone image. Finally, hot plate baking was performed at 150 °C for 2 minutes to complete the process.

[0111] The thickness of the residual resist on the exposed pads was measured using an ellipsometer. The remaining thickness was measured for each exposure dose and graphed as a function of the exposure dose to measure the sensitivity. After measuring the LER from the FE-SEM image, the sensitivity and line edge roughness were evaluated according to the following criteria, and the results are shown in Table 2.

[0112] [Sensitivity evaluation criteria] -A: Less than 16 mJ / cm 2 Less than -B: 16 mJ / cm or more 2 Or more

[0113] [LER evaluation criteria] -○: 2 nm or less -△: More than 2 nm and 5 nm or less -X: More than 5 nm

[0114] Evaluation 2: Resolution (CD) evaluation For the pattern wafer on which the process was completed, a Line / Space CD pattern was formed. Thereafter, it was transferred to a CD-SEM measuring device (GC-9380, Hitachi) to measure the CD (Critical Dimension) size at the site where the half-pitch of the mask pattern was 14 nm, and the minimum value of the space CD, which is the interval between lines, is shown in Table 2.

[0115]

Table 2

[0116] From the results in Table 2, it can be confirmed that the patterns formed using the semiconductor photoresist compositions according to Examples 1 to 9 exhibit excellent sensitivity, LER, and resolution characteristics as compared with Comparative Examples 1 to 3.

[0117] As described above, specific embodiments of the present invention have been described and illustrated. However, the present invention is not limited to the described embodiments, and it is obvious to those having ordinary knowledge in this technical field that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modified examples or variations should not be individually understood from the technical spirit or viewpoint of the present invention, and the modified embodiments belong to the scope of the claims of the present invention.

Explanation of Signs

[0118] 100... Substrate, 102... Thin film, 104... Underlayer resist film, 106... Photoresist film, 106a... Exposed region, 106b... Unexposed region, 108... Photoresist pattern, 112... Organic film pattern, 110... Patterned mask, 114... Thin film pattern.

Claims

1. An organometallic compound containing Sn; A carboxylic acid compound; At least one of a sulfonic acid compound and a phosphonic acid compound; and A solvent A composition for a semiconductor photoresist, comprising the same.

2. The carboxylic acid compound: at least one of the sulfonic acid compound and the phosphonic acid compound is contained in a weight ratio of 1:0.001 to 1:10, the composition for a semiconductor photoresist according to Claim 1.

3. The carboxylic acid compound is the one represented by the following Chemical Formula 1, the composition for a semiconductor photoresist according to Claim 1: 【Chemical 1】 In the Chemical Formula 1, R １ is an amino group, halogen, hydroxy group, carboxyl group, substituted or unsubstituted C1-C20 alkyl group, substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C2-C20 alkenyl group, substituted or unsubstituted C2-C20 alkynyl group, substituted or unsubstituted C6-C30 aryl group, or substituted or unsubstituted C7-C30 arylalkyl group, L １ and L ２ are each independently a single bond, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C6-C30 arylene group, or a combination thereof, X １ is a single bond, O, S or NR ２ (R ２ is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), m1 is an integer of 1 or more.

4. The sulfonic acid compound is the one represented by the following Chemical Formula 2, the composition for a semiconductor photoresist according to Claim 1: ​ In the Chemical Formula 2, R ３ is an amino group, a halogen, a hydroxy group, a carboxyl group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C7-C30 arylalkyl group, L ３ and L ４ are each independently a single bond, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C6-C30 arylene group, or a combination thereof, X ２ is a single bond, O, S or NR ４ (R ４ is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), m2 is an integer of 1 or more.

5. The phosphonic acid compound is the one represented by the following Chemical Formula 3, the composition for a semiconductor photoresist according to Claim 1: [Chemical Formula 3] In the Chemical Formula 3, R ５ is an amino group, a halogen, a hydroxy group, a carboxyl group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C7-C30 arylalkyl group, L ５ and L ６ are each independently a single bond, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C6-C30 arylene group, or a combination thereof, X ３ is a single bond, O, S or NR ６ (R ６ is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), m3 is an integer of 1 or more.

6. The carboxylic acid compound is at least one selected from the compounds listed in the following Group 1, the composition for a semiconductor photoresist according to Claim 1: 【Chemical Formula 4】

7. The sulfonic acid compound and the phosphonic acid compound are at least one selected from the compounds listed in the following Group 2, the composition for a semiconductor photoresist according to Claim 1: [Chemical Formula 5]

8. The carboxylic acid compound and at least one of the sulfonic acid compound and the phosphonic acid compound are contained in a total amount of 0.001 to 10% by weight based on 100% by weight of the composition for a semiconductor photoresist, the composition for a semiconductor photoresist according to Claim 1.

9. The carboxylic acid compound and at least one of the sulfonic acid compound and the phosphonic acid compound are contained in a total amount of 0.1 to 5% by weight based on 100% by weight of the composition for a semiconductor photoresist, the composition for a semiconductor photoresist according to Claim 1.

10. The organometallic compound containing Sn is contained in an amount of 0.5% to 30% by weight based on 100% by weight of the composition for a semiconductor photoresist, the composition for a semiconductor photoresist according to Claim 1.

11. The composition for a semiconductor photoresist according to claim 1, further comprising an additive which is a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, or a combination thereof.

12. The composition for a semiconductor photoresist according to claim 1, wherein the Sn-containing organometallic compound contains at least one of an organic oxy group and an organic carbonyloxy group.

13. The composition for a semiconductor photoresist according to claim 1, wherein the Sn-containing organometallic compound is represented by the following chemical formula 4: [Chemical Formula 6] In the chemical formula 4, R ７ is selected from a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C6-C30 arylalkyl group, R ８ ~R １０ each independently represents a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 arylalkyl group, alkoxo and aryloxo (-OR ａ , where R ａ represents a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), a carboxyl group (-O(CO)R ｂ , R ｂ represents hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an alkylamide or dialkylamide (-NR ｃ R ｄ , where R ｃ and R ｄ each independently represent hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an amidato (-NR ｅ (COR ｆ ), where R ｅ and R ｆ is, independently, hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidinato (—NR ｇ C(NR ｈ )R ｉ , where R ｇ , R ｈ and R ｉ are, independently, hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (—SR ｊ , where R ｊ is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof) or a thiocarboxyl group (—S(CO)R ｋ , R ｋ is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), and R ８ to R １０ at least one of which is alkoxo and aryloxo (—OR ａ , where R ａ is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), a carboxyl group (—O(CO)R ｂ , R ｂ is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an alkylamide or dialkylamide (—NR ｃ R ｄ , where R ｃ and R ｄ are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an amidato (—NR ｅ (COR ｆ ), where R ｅ and R ｆ are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an amidinato (—NR ｇ C(NR ｈ )R ｉ , where R ｇ , R ｈ and R ｉ is, independently of one another, hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (—SR ｊ , where R ｊ is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof) and thiocarboxyl group (—S(CO)R ｋ , R ｋ is selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof).

14. Said R ８ to R １０ At least one of them is alkoxo and aryloxo (—OR ａ , where R ａ is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), and a carboxyl group (—O(CO)R ｂ , R ｂ is selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof). The composition for a semiconductor photoresist according to claim 13.

15. Said R ７ is a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C4-C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof, R ａ is a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof, R ｂ is a hydrogen, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof, the composition for a semiconductor photoresist according to claim 13.

16. The composition for a semiconductor photoresist according to claim 1, wherein the Sn-containing organometallic compound is represented by the following chemical formula 5 or chemical formula 6: 【Chemical Formula 7】 In the chemical formula 5, R １１ is a C1-C31 hydrocarbyl group, where 0 < z ≦ 2 and 0 < (z + x) ≦ 4; 【Chemical 8】 In the chemical formula 6, R １２ is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C4-C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof, X is sulfur (S), selenium (Se), or tellurium (Te), Y is -OR ｌ or -OC(=O)R ｍ and Said R ｌ is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof, R ｍ is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof, and a1, b1, c1, and d1 are each independently an integer from 1 to 20.

17. Forming an etching target film on a substrate; Applying the composition for a semiconductor photoresist according to any one of claims 1 to 16 on the etching target film to form a photoresist film; Patterning the photoresist film to form a photoresist pattern; And etching the etching target film using the photoresist pattern as an etching mask. A pattern forming method comprising the steps.

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