Semiconductor photoresist compositions and methods of forming patterns using the composition

Abstract

To provide a semiconductor photoresist composition having excellent sensitivity and line edge roughness (LER) characteristics and improved coatability, and a method of forming patterns using the composition.SOLUTION: The present invention relates to a semiconductor photoresist composition comprising an organic tin compound including a hydrolyzable ligand substituted with at least one deuterium, and a solvent, and a method of forming patterns using the composition.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a semiconductor photoresist composition and a pattern forming method using the same. [Background technology]

[0002] EUV (extreme ultraviolet) lithography is attracting attention as one of the elemental technologies for manufacturing next-generation semiconductor devices. EUV lithography is a pattern formation technology that uses EUV light with a wavelength of 13.5 nm as the exposure light source. It has been demonstrated that EUV lithography can form extremely fine patterns (e.g., 20 nm or less) during the exposure step in the semiconductor device manufacturing process.

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

[0004] Intrinsic image blur due to acid-catalyzed reactions occurring in these polymeric photoresists limits resolution at small feature sizes, a long-known fact in electron beam (e-beam) lithography. Chemically amplified (CA) photoresists, designed for high sensitivity, can experience additional difficulties under EUV exposure, in part because their typical elemental makeup reduces the photoresist's absorbance at 13.5 nm wavelengths, thereby reducing sensitivity.

[0005] CA photoresists can also experience roughness issues at small feature sizes, and experiments have shown that line edge roughness (LER) increases as the photospeed decreases, partly due to the nature of the acid-catalyzed process. Due to the shortcomings and problems of CA photoresists, there is a demand in the semiconductor industry for new types of high-performance photoresists.

[0006] To overcome the drawbacks of the chemically amplified organic photosensitive compositions described above, inorganic photosensitive compositions have been developed. Inorganic photosensitive compositions are primarily used in negative-tone patterning, where they are resistant to removal by developer compositions due to chemical modification through a non-chemically amplified mechanism. Inorganic compositions contain inorganic elements with higher EUV absorption than hydrocarbons, ensuring sensitivity even in non-chemically amplified mechanisms. They are also known to have reduced sensitivity to the stochastic effect, resulting in fewer line edge roughness and fewer defects.

[0007] Inorganic photoresists based on peroxopolyacids of tungsten and tungsten mixed with niobium, titanium, and / or tantalum have been reported for patterning radiation-sensitive materials (US Pat. No. 5,061,599; H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298-300, 1986).

[0008] These materials have been effective for patterning large features in bilayer configurations with deep UV, x-ray, and electron beam sources. More recently, impressive performance has been demonstrated when using cationic hafnium metal oxide sulfate (HfSOx) materials with peroxocomplexing agents to image 15 nm half-pitch (HP) patterns with projection EUV exposure (US 2011-0045406; 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 exhibits the best performance of any non-CA photoresist and has photospeeds 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, resulting in poor shelf-life stability. Second, because they are complex mixtures, it is difficult to modify their structure to improve performance. Third, they must be developed using extremely high-concentration solutions, such as 25 wt% TMAH (tetramethylammonium hydroxide).

[0009] Recently, active research has been conducted on tin-containing molecules due to their excellent absorption of extreme ultraviolet light. In the case of organotin polymers, one such polymer, alkyl ligands are dissociated by light absorption or the secondary electrons generated by the absorption, and crosslinking with surrounding chains through oxo bonds enables negative-tone patterning that is resistant to removal by organic developers. These organotin polymers have demonstrated dramatic improvements in sensitivity while maintaining resolution and line edge roughness, but further improvements in their patterning properties are required for commercialization. Summary of the Invention [Problem to be solved by the invention]

[0010] An embodiment of the present invention provides a semiconductor photoresist composition that has excellent sensitivity and line edge roughness (LER) characteristics and improved coatability.

[0011] Another embodiment of the present invention provides a method for forming a pattern using the semiconductor photoresist composition. [Means for solving the problem]

[0012] A semiconductor photoresist composition according to one embodiment of the present invention includes an organotin compound including at least one deuterium-substituted hydrolyzable ligand and a solvent.

[0013] A pattern forming method according to another embodiment of the present invention includes the steps of forming a film to be etched on a substrate, applying the above-described semiconductor photoresist composition on the film to be etched and heating at a temperature of 110°C to 180°C to form a photoresist film, exposing and developing the photoresist film to form a photoresist film having a photoresist pattern formed thereon, and etching the film to be etched using the photoresist pattern as an etching mask. [Effects of the Invention]

[0014] A semiconductor photoresist composition according to one embodiment of the present invention can achieve excellent sensitivity and excellent LER characteristics, and a photoresist film to which the photoresist composition is applied can maintain excellent coating properties even in high-temperature processes. [Brief explanation of the drawings]

[0015] [Figure 1] 1A to 1C are cross-sectional views illustrating a method for forming a pattern using a semiconductor photoresist composition according to an embodiment. DETAILED DESCRIPTION OF THE INVENTION

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

[0017] In order to clarify the present description, parts unnecessary for the description have been omitted, and the same or similar components have been given the same reference numerals throughout the specification. Furthermore, the size and thickness of each component shown in the drawings are arbitrarily shown for the convenience of explanation, and the present description is not necessarily limited to those shown in the drawings.

[0018] In the drawings, the thickness of multiple layers and regions is exaggerated to clearly show them. For ease of explanation, the thickness of some layers and regions is exaggerated in the drawings. When a layer, film, region, plate, or other part is said to be "on" another part, this does not only mean that it is "directly on" that other part, but also includes the case where there is another part between them.

[0019] In this description, "substituted" means that a hydrogen atom is replaced with a deuterium atom, a halogen group, a hydroxy group, a carboxyl group, a thiol group, a cyano group, a nitro group, -NRR' (wherein R and R' are each independently hydrogen, a substituted or unsubstituted saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted saturated or unsaturated alicyclic hydrocarbon group having 3 to 30 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms), -SiRR'R'' (wherein R, R', and R'' are each independently hydrogen, a substituted or unsubstituted "Unsubstituted" means that the hydrogen atoms are not substituted with other substituents and remain as hydrogen atoms.

[0020] As used herein, unless otherwise defined, the term "alkyl group" refers to 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 an alkyl group having 1 to 8 carbon atoms. For example, the alkyl group may be an alkyl group having 1 to 7 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. For example, the alkyl group having 1 to 5 carbon atoms 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, a tert-butyl group, or a 2,2-dimethylpropyl group.

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

[0023] The cycloalkyl group may be a cycloalkyl group having 3 to 8 carbon atoms, for example, a cycloalkyl group having 3 to 7 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 3 to 5 carbon atoms, or a cycloalkyl group having 3 to 4 carbon atoms. For example, the cycloalkyl group may be, but is not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

[0024] As used herein, "aliphatically unsaturated organic group" refers to a hydrocarbon group containing bonds between carbon atoms in the molecule that are double bonds, triple bonds, or a combination thereof.

[0025] The aliphatic unsaturated organic group may be an aliphatic unsaturated organic group having 2 to 8 carbon atoms. For example, the aliphatic unsaturated organic group may be an aliphatic unsaturated organic group having 2 to 7 carbon atoms, an aliphatic unsaturated organic group having 2 to 6 carbon atoms, an aliphatic unsaturated organic group having 2 to 5 carbon atoms, or an aliphatic unsaturated organic group having 2 to 4 carbon atoms. For example, the aliphatic unsaturated organic group having 2 to 4 carbon atoms 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" refers to a cyclic substituent in which all elements have p-orbitals and these p-orbitals form conjugation, including 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" refers to an aryl group containing at least one heteroatom selected from the group consisting of N, O, S, P, and Si. Two or more heteroaryl groups may be directly linked via a sigma bond, or, if the heteroaryl group contains two or more rings, the two or more rings may be fused to each other. If the heteroaryl group is a fused ring, each ring may contain 1 to 3 heteroatoms.

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

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

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

[0031] A composition for semiconductor photoresist according to one embodiment of the present invention may include an organotin compound including at least one deuterium-substituted hydrolyzable ligand and a solvent.

[0032] When the compound has a deuterium-substituted ligand, the coating property is improved in a high temperature process, and the sensitivity of the photoresist to which it is applied is improved.

[0033] The organotin compound is represented by the following chemical formula 1:

[0034] [ka] R 1is selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms; X is a hydrolyzable group containing at least one deuterium; n is an integer from 1 to 3.

[0035] In one example, X is alkoxy and aryloxy (—OR a , where R a is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), a carboxyl group (-O(CO)R b , R b is hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylamide or dialkylamide (-NR c R d , where R c and R d are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), amidato (-NR e (COR f ), where R e and R fare each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), amidinato (-NR g C(NR h )R i , where R g , R h and R i are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylthio and arylthio (-SR j , where R j is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), and a thiocarboxyl group (-S(CO)R k , R k is selected from hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; R a and R j are each independently substituted with at least one deuterium; R b and R k are each independently deuterium or substituted with at least one deuterium; Rc and R d At least one of R e and R f At least one of; and R g , R h and R i At least one of each independently is deuterium or is substituted with at least one deuterium.

[0036] As a specific example, X is alkoxy and aryloxy (—OR a , where R a is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), a carboxyl group (-O(CO)R b , R b is hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), and amidato (-NR e (COR f ), where R e and R f are each independently selected from hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; R a are each independently substituted with at least one deuterium; R b are each independently deuterium or substituted with at least one deuterium; R e and R f At least one of is deuterium or is substituted with at least one deuterium.

[0037] For example, the R a and R j are each independently a methyl group substituted with at least one deuterium, an ethyl group substituted with at least one deuterium, a propyl group substituted with at least one deuterium, a butyl group substituted with at least one deuterium, an isopropyl group substituted with at least one deuterium, a tert-butyl group substituted with at least one deuterium, a tert-pentyl group substituted with at least one deuterium, a 2,2-dimethylpropyl group substituted with at least one deuterium, a cyclopropyl group substituted with at least one deuterium, a cyclobutyl ... a cyclopentyl group, a cyclohexyl group substituted with at least one deuterium, an ethenyl group substituted with at least one deuterium, a propenyl group substituted with at least one deuterium, a butenyl group substituted with at least one deuterium, an ethynyl group substituted with at least one deuterium, a propynyl group substituted with at least one deuterium, a butynyl group substituted with at least one deuterium, a phenyl group substituted with at least one deuterium, a tolyl group substituted with at least one deuterium, a xylene group substituted with at least one deuterium, a benzyl group substituted with at least one deuterium, or a combination thereof; R b and R keach independently represents a deuterium, a methyl group substituted with at least one deuterium, an ethyl group substituted with at least one deuterium, a propyl group substituted with at least one deuterium, a butyl group substituted with at least one deuterium, an isopropyl group substituted with at least one deuterium, a tert-butyl group substituted with at least one deuterium, a tert-pentyl group substituted with at least one deuterium, a 2,2-dimethylpropyl group substituted with at least one deuterium, a cyclopropyl group substituted with at least one deuterium, a cyclobutyl group substituted with at least one deuterium, a cyclopentyl group, a cyclohexyl group substituted with at least one deuterium, an ethenyl group substituted with at least one deuterium, a propenyl group substituted with at least one deuterium, a butenyl group substituted with at least one deuterium, an ethynyl group substituted with at least one deuterium, a propynyl group substituted with at least one deuterium, a butynyl group substituted with at least one deuterium, a phenyl group substituted with at least one deuterium, a tolyl group substituted with at least one deuterium, a xylene group substituted with at least one deuterium, a benzyl group substituted with at least one deuterium, or a combination thereof; R c , R d , R e , R f , R g , R h and R iare each independently hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-pentyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted ethenyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylene, substituted or unsubstituted benzyl, or a combination thereof; R c and R d At least one of R e and R f At least one of; and R g , R h and R iat least one of which is independently deuterium, a methyl group substituted with at least one deuterium, an ethyl group substituted with at least one deuterium, a propyl group substituted with at least one deuterium, a butyl group substituted with at least one deuterium, an isopropyl group substituted with at least one deuterium, a tert-butyl group substituted with at least one deuterium, a tert-pentyl group substituted with at least one deuterium, a 2,2-dimethylpropyl group substituted with at least one deuterium, a cyclopropyl group substituted with at least one deuterium, a cyclobutyl group substituted with at least one deuterium, The alkyl group may be a substituted cyclopentyl group, a cyclohexyl group substituted with at least one deuterium, an ethenyl group substituted with at least one deuterium, a propenyl group substituted with at least one deuterium, a butenyl group substituted with at least one deuterium, an ethynyl group substituted with at least one deuterium, a propynyl group substituted with at least one deuterium, a butynyl group substituted with at least one deuterium, a phenyl group substituted with at least one deuterium, a tolyl group substituted with at least one deuterium, a xylene group substituted with at least one deuterium, a benzyl group substituted with at least one deuterium, or a combination thereof.

[0038] The deuterium substitution rate of the hydrolyzable ligand may be 1 to 100%.

[0039] For example, the deuterium substitution rate may be 5 to 90%, specifically 10 to 75%, and more specifically 20 to 65%.

[0040] In this specification, the deuterium substitution rate means [(the number of deuterium atoms contained in the ligand) / (the maximum number of hydrogen atoms that the ligand can have)].

[0041] As used herein, N% deuterated means that N% of the available hydrogens in the structure are replaced with deuterium.

[0042] For example, 100% substitution of acetamide with deuterium means that all four hydrogen atoms of acetamide, excluding the hydrogen atom at the bonding position with the metal, are substituted with deuterium atoms.

[0043] As used herein, the degree of deuteration is measured by nuclear magnetic resonance spectroscopy ( 1 This can be confirmed by known methods such as H-NMR and GC / MS.

[0044] The hydrolyzable ligand may be one or more functional groups derived from propionic acid, 4-methyl-2-pentanol (MIBC), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), furoic acid, diethylamine, methyl isobutyrate, etc.

[0045] According to one embodiment, the composition for semiconductor photoresist includes the organotin compound having a deuterium-substituted hydrolyzable ligand, thereby improving the sensitivity of the photoresist.

[0046] The organotin compound has a strong absorption of extreme ultraviolet light at 13.5 nm and is highly sensitive to light having high energy.

[0047] In one embodiment, the semiconductor photoresist composition may contain the organotin compound in an amount of, but not limited to, 0.5% by weight to 30% by weight, for example, 1% by weight to 30% by weight, 1% by weight to 25% by weight, for example, 1% by weight to 20% by weight, for example, 1% by weight to 15% by weight, for example, 1% by weight to 10% by weight, or for example, 1% by weight to 5% by weight, based on 100% by weight of the semiconductor photoresist composition. When the organotin compound is contained in an amount within the above range, the storage stability and etching resistance of the semiconductor photoresist composition are improved, and resolution characteristics are improved.

[0048] The semiconductor photoresist composition according to one embodiment of the present invention contains the organotin compound described above, and thus can provide a semiconductor photoresist composition having excellent sensitivity and pattern formability.

[0049] The solvent included in the semiconductor photoresist composition according to an embodiment may be an organic solvent, and examples thereof may include, but are not limited to, 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), and mixtures thereof.

[0050] In one embodiment, the semiconductor photoresist composition may further include a resin in addition to the organotin compound and solvent.

[0051] The resin may be a phenolic resin containing at least one aromatic moiety listed in Group 2 below.

[0052] [ka]

[0053] The resin may have a weight average molecular weight of 500 to 20,000.

[0054] The resin may be contained in an amount of 0.1% by weight to 50% by weight based on the total content of the semiconductor photoresist composition.

[0055] When the resin is contained within the above content range, excellent etching resistance and heat resistance can be obtained.

[0056] Meanwhile, a semiconductor photoresist composition according to an embodiment preferably comprises the above-described organotin compound, solvent, and resin. However, the semiconductor photoresist composition according to the above-described embodiment may further include additives, such as surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0057] The surfactant may be, for example, but not limited to, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, or a combination thereof.

[0058] Examples of crosslinking agents include, but are not limited to, melamine-based crosslinking agents, substituted urea-based crosslinking agents, acrylic-based crosslinking agents, epoxy-based crosslinking agents, and polymer-based crosslinking agents. Examples of crosslinking agents having at least two crosslink-forming substituents that can be used include 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, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, and methoxymethylated thiourea.

[0059] The leveling agent is used to improve coating flatness during printing, and any known leveling agent that is commercially available can be used.

[0060] The organic acid can be, but is not limited to, p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, sulfonium fluoride salts, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or combinations thereof.

[0061] The quencher can be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0062] The amount of these additives used can be easily adjusted depending on the desired physical properties, and they may also be omitted.

[0063] The semiconductor photoresist composition may further contain a silane coupling agent as an additive to enhance adhesion to a substrate (e.g., to improve the adhesive strength of the semiconductor photoresist composition to a substrate). Examples of the silane coupling agent include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; and silane compounds containing a carbon-carbon unsaturated bond, such as trimethoxy[3-(phenylamino)propyl]silane.

[0064] The semiconductor photoresist composition may not cause pattern collapse even when forming a pattern having a high aspect ratio. Therefore, the composition 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 70 nm, for example, a photoresist process using light with a width of 5 nm to 50 nm, for example, a photoresist process using light with a wavelength of 5 nm to 40 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, 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, or for example, a photoresist process using light with a wavelength of 5 nm to 20 nm. Therefore, by using the semiconductor photoresist composition according to one embodiment, extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5 nm can be realized.

[0065] According to another embodiment, there is provided a method for forming a pattern using the semiconductor photoresist composition. For example, the pattern formed may be a photoresist pattern.

[0066] A pattern forming method according to one embodiment includes the steps of: forming a film to be etched on a substrate; applying the above-described semiconductor photoresist composition on the film to be etched and heating at a temperature of 110°C to 180°C to form a photoresist film; exposing and developing the photoresist film to form a photoresist film having a photoresist pattern formed thereon; and etching the film to be etched using the photoresist pattern as an etching mask.

[0067] Hereinafter, a method for forming a pattern using the semiconductor photoresist composition will be described with reference to Fig. 1. Fig. 1 is a cross-sectional view illustrating a method for forming a pattern using the semiconductor photoresist composition according to the present invention.

[0068] Referring to FIG. 1(a), first, an etching target is prepared. An example of the etching target may be a thin film 102 formed on a semiconductor substrate 100. The following description will be limited to the case where the etching target is the thin film 102. The surface of the thin film 102 is cleaned to remove contaminants remaining on the thin film 102. The thin film 102 may be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film.

[0069] Next, a composition for forming a resist underlayer film is coated by spin coating on the surface of the cleaned thin film 102 to provide a resist underlayer film 104. However, the present invention is not limited thereto, and various known coating methods, such as spray coating, dip coating, knife edge coating, and printing methods, such as inkjet printing and screen printing, may also be used.

[0070] The step of coating the resist underlayer film can be omitted, and the following description will be made of the case where the resist underlayer film is coated.

[0071] Thereafter, drying and baking steps are performed to form a resist underlayer film 104 on the thin film 102. The baking treatment can be performed at about 100 to about 500°C, for example, about 100 to about 300°C.

[0072] The resist underlayer film 104 is formed between the substrate 100 and the photoresist film 106, and can prevent non-uniformity of the photoresist linewidth and disruption of pattern formability when radiation reflected from the interface between the substrate 100 and the photoresist film 106 or from an interlayer hard mask is scattered into unintended photoresist regions.

[0073] 1(b), the semiconductor photoresist composition is coated on the resist underlayer film 104 to form a photoresist film 106. The photoresist film 106 may be formed by coating the semiconductor photoresist composition on a thin film 102 formed on a substrate 100 and then curing the composition through a heat treatment process.

[0074] More specifically, the step of forming a pattern using the semiconductor photoresist composition may include a step of applying the semiconductor photoresist composition onto the substrate 100 on which the thin film 102 has been 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.

[0075] The semiconductor photoresist composition has already been explained in detail, so a duplicate explanation will be omitted.

[0076] Next, a first baking process is performed to heat the substrate 100 on which the photoresist film 106 is formed. The first baking process can be performed at a temperature of about 110°C to about 180°C.

[0077] The first baking step can be carried out at a temperature of, for example, 130°C to 180°C, specifically 130°C to 160°C.

[0078] The root mean square roughness (R q ;root mean square roughness) may be less than 0.4.

[0079] The photoresist film may also contain Sn-O-Sn and Sn-OD bonds.

[0080] Referring to FIG. 1(c), the photoresist film 106 is selectively exposed to light using a patterned mask 110.

[0081] For example, examples of light that can be used in the exposure process include light with short wavelengths such as activation irradiation i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), as well as light with high energy wavelengths such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0082] More specifically, the exposure light in 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) or E-Beam (electron beam).

[0083] The exposed region 106b of the photoresist film 106 has a different solubility from the unexposed region 106a of the photoresist film 106 by forming a polymer through a crosslinking reaction such as condensation between organometallic compounds.

[0084] Meanwhile, after exposure, the photoresist pattern may contain Sn-O-Sn and Sn-OD bonds.

[0085] 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 106b of the photoresist film 106 becomes less soluble in a developer.

[0086] 1(d) shows a photoresist pattern 108 formed by dissolving and removing the photoresist film 106a corresponding to the unexposed region using a developer. Specifically, the photoresist film 106a corresponding to the unexposed region is dissolved and removed using an organic solvent such as 2-heptanone, thereby completing the photoresist pattern 108 corresponding to the negative tone image.

[0087] 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, and combinations thereof.

[0088] However, the photoresist pattern according to an embodiment is not limited to being formed as a negative tone image, and may also be formed as a positive tone image. In this case, developers that can be used to form a positive tone image include quaternary ammonium hydroxide compositions such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof.

[0089] As described above, the photoresist pattern 108 formed by exposure to light having a wavelength such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), or ArF excimer laser (wavelength 193 nm), as well as high-energy light such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-beam (electron beam), may have a thickness of 5 nm to 100 nm. For example, the photoresist pattern 108 may 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, or 5 nm to 10 nm.

[0090] Meanwhile, the photoresist pattern 108 may have a half-pitch of about 50 nm or less, e.g., 40 nm or less, e.g., 30 nm or less, e.g., 20 nm or less, e.g., 10 nm or less, and a pitch with a line width roughness of about 5 nm or less, about 3 nm or less, about 2 nm or less, or about 1 nm or less.

[0091] According to yet another embodiment, there is provided a photoresist film manufactured by the above-described patterning method.

[0092] Next, the resist underlayer 104 is etched using the photoresist pattern 108 formed on the photoresist film as an etching mask. This etching process forms an organic layer pattern 112. The formed organic layer pattern 112 may also have a width corresponding to the photoresist pattern 108.

[0093] 1(e), the photoresist pattern 108 is used as an etching mask to etch the exposed thin film 102. As a result, the thin film is formed into a thin film pattern 114.

[0094] The thin film 102 can be etched by dry etching using an etching gas, such as CHF3, CF4, Cl2, BCl3, or a mixture thereof.

[0095] The thin film pattern 114 formed using the photoresist pattern 108 formed by the previous exposure process using an EUV light source may have a width corresponding to the photoresist pattern 108. For example, it may have a width of 5 nm to 100 nm, similar to the photoresist pattern 108. For example, the thin film pattern 114 formed by the exposure process using an EUV light source may 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, or 5 nm to 20 nm, similar to the photoresist pattern 108, and more specifically, may have a width of 20 nm or less. [Example]

[0096] The present invention will be described in more detail below with reference to examples of preparing the above-mentioned semiconductor photoresist composition, but the technical features of the present invention are not limited to these examples.

[0097] (Synthesis of organometallic compounds) Synthesis Example 1 In a 250 mL two-neck round-bottom flask, 20 g (51.9 mmol) of Ph3SnCl was dissolved in 70 mL of THF and the temperature was lowered to 0°C in an ice bath. Then, butylmagnesium chloride (BuMgCl) 1 M THF solution (62.3 mmol) was slowly added dropwise. After the addition was completed, the mixture was stirred at 25°C for 12 hours to obtain the compound represented by the following chemical formula 2a.

[0098] Then, 10 g (24.6 mmol) of the compound of formula 2a was dissolved in 50 mL of CHCl, and 3 equivalents (73.7 mmol) of 2 M hydrochloric acid solution (in diethyl ether) was slowly added dropwise for 30 minutes at -78°C. After stirring at 25°C for 12 hours, the solvent was concentrated and distilled under vacuum to obtain a compound represented by formula 2b.

[0099] Then, 25 mL of D-substituted acetic acid was slowly added dropwise to 10 g (25.6 mmol) of the compound of Formula 2b at 25°C, and the mixture was heated to reflux for 12 hours. After the temperature was raised to 25°C, the acetic acid was distilled under vacuum to finally obtain the compound represented by Formula 2 below.

[0100] [ka]

[0101] Synthesis Example 2 A compound represented by the following Chemical Formula 3 was obtained in the same manner as in Synthesis Example 1, except that D (deuterium)-substituted benzoic acid was used instead of D (deuterium)-substituted acetic acid.

[0102] [ka]

[0103] Synthesis Example 3 A compound represented by the following Chemical Formula 4 was obtained in the same manner as in Synthesis Example 1, except that D-substituted diethylamine was used instead of D-substituted acetic acid.

[0104] [ka]

[0105] Synthesis Example 4 A compound represented by the following Chemical Formula 5 was obtained in the same manner as in Synthesis Example 1, except that D-substituted 4-methyl-2-pentanol was used instead of D-substituted acetic acid.

[0106] [ka]

[0107] Synthesis Example 5 A compound represented by the following Chemical Formula 6 was obtained in the same manner as in Synthesis Example 1, except that D (deuterium)-substituted propylene glycol ether was used instead of D (deuterium)-substituted acetic acid.

[0108] [ka]

[0109] Synthesis Example 6 A compound represented by the following Formula 7 was obtained in the same manner as in Synthesis Example 1, except that acetic acid was used instead of D (deuterium)-substituted acetic acid.

[0110] [ka]

[0111] Synthesis Example 7 A compound represented by the following formula 8 was obtained in the same manner as in Synthesis Example 1, except that benzoic acid was used instead of D (deuterium)-substituted acetic acid.

[0112] [ka]

[0113] Synthesis Example 8 A compound represented by the following formula 9 was obtained in the same manner as in Synthesis Example 1, except that diethylamine was used instead of D (deuterium)-substituted acetic acid.

[0114] [ka]

[0115] Synthesis Example 9 A compound represented by the following Chemical Formula 10 was obtained in the same manner as in Synthesis Example 1, except that 4-methyl-2-pentanol was used instead of D (deuterium)-substituted acetic acid.

[0116] [ka]

[0117] Synthesis Example 10 A compound represented by the following Chemical Formula 11 was obtained in the same manner as in Synthesis Example 1, except that propylene glycol ether was used instead of D (deuterium)-substituted acetic acid.

[0118] [ka]

[0119] (Production of semiconductor photoresist composition) Examples 1 to 5 and Comparative Examples 1 to 5 The organotin compounds obtained in Synthesis Examples 1 to 10 were dissolved in a solvent (propylene glycol methyl ether acetate: PGMEA or 4-methyl-2-pentanol: MIBC) shown in Table 1 below at a concentration of 3 wt %, and the solution was filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to prepare semiconductor photoresist compositions.

[0120] [Table 1]

[0121] Evaluation 1: Sensitivity evaluation Each of the photoresist compositions according to the Examples and Comparative Examples was spin-coated at 1500 rpm for 60 seconds onto a 200 mm circular silicon wafer whose surface had been deposited with HMDS, and baked at 110°C for 60 seconds (post-apply bake, PAB).

[0122] The wafer coated with the photoresist composition was then exposed to EUV light, and the pad exposure time was adjusted so that an increased EUV dose was applied to each pad.

[0123] The resist and substrate were then exposed and baked on a hot plate at 170°C for 60 seconds. The baked film was then immersed in a developer (2-heptanone) for 30 seconds, washed in the developer for 10 seconds to remove the unexposed coating, and finally baked on a hot plate at 150°C for 2 minutes to form a final L / S pattern (1:1).

[0124] The thickness of the remaining resist on the exposed pad was measured using an ellipsometer. The remaining thickness was measured for each exposure dose and graphed as a function of exposure dose to determine sensitivity. The results are shown in Table 2.

[0125] Evaluation 2: Process stability evaluation The photoresist compositions according to the Examples and Comparative Examples were spin-coated at 1500 rpm for 60 seconds on a 200 mm circular silicon wafer whose surface had been deposited with HMDS, and then baked at temperatures of 130°C and 160°C for 60 seconds (post-apply bake, PAB) to form thin films. The surface roughness of the thin films was measured from images taken with an atomic force microscopy (AFM) using software (e.g., an optical profiler), and the results are shown in Table 2 below.

[0126] If the Rq value, which indicates the surface roughness of the coating thin film, is less than 0.4 and the change in the surface roughness value of the thin film is small even when the temperature rises to a high level, it means that the coating has excellent process stability.

[0127] The rate of change in surface roughness value was calculated using the following formula 1.

[0128] [Formula 1] Rate of change in surface roughness value = [{Rq when PAB is performed at 160°C) - (Rq when PAB is performed at 130°C)} / Rq when PAB is performed at 130°C)] × 100

[0129] [Table 2]

[0130] From the results in Table 2, it can be seen that the patterns formed using the semiconductor photoresist compositions of Examples 1 to 5 exhibit superior sensitivity characteristics compared to Comparative Examples 1 to 5, and maintain a surface roughness of less than 0.4 even when subjected to a high-temperature process, and the change rate of the film surface roughness value due to temperature increase is small, thereby ensuring excellent coatability.

[0131] Although specific embodiments of the present invention have been described and illustrated above, it will be apparent to those skilled in the art that the present invention is not limited to the described embodiments and that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modifications and variations should not be understood individually from the technical spirit and perspective of the present invention, and the modified embodiments should be considered to fall within the scope of the claims of the present invention. [Explanation of symbols]

[0132] 100...substrate, 102...thin film, 104...resist underlayer film, 106...photoresist film, 106a...unexposed region, 106b...exposed region, 108...photoresist pattern, 112...organic film pattern, 110...patterned mask, 114...thin film pattern.

Claims

1. an organotin compound containing at least one deuterium-substituted hydrolyzable ligand; and A composition for semiconductor photoresist, comprising a solvent.

2. 2. The composition for semiconductor photoresist of claim 1, wherein the organotin compound is represented by the following chemical formula 1: 【Chemical 1】 R １ is selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms; X is a hydrolyzable group containing at least one deuterium; n is an integer from 1 to 3.

3. The X is alkoxy and aryloxy (—OR ａ , where R ａ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), a carboxyl group (—O(CO)R ｂ , R ｂ is hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylamide or dialkylamide (—NR ｃ R ｄ , where R ｃ and R ｄ are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), amidate (—NR ｅ (COR ｆ ), where R ｅ and R ｆ are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), amidinato (—NR ｇ C (NR ｈ ) R ｉ , where R ｇ , R ｈ and R ｉ are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), alkylthio and arylthio (-SR ｊ , where R ｊ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), and a thiocarboxyl group (—S(CO)R ｋ , R ｋ is selected from hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; The R ａ and the R ｊ are each independently substituted with at least one deuterium; The R ｂ and the R ｋ are each independently deuterium or substituted with at least one deuterium; The R ｃ and the R ｄ At least one of R ｅ and R ｆ and at least one of the R ｇ , the R ｈ and the R ｉ 3. The semiconductor photoresist composition according to claim 2, wherein at least one of each independently is deuterium or is substituted with at least one deuterium.

4. The X is alkoxy and aryloxy (—OR ａ , where R ａ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), a carboxyl group (—O(CO)R ｂ , R ｂ is hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), and amidato (—NR ｅ (COR ｆ ), where R ｅ and R ｆ are each independently selected from hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; The R ａ are each independently substituted with at least one deuterium; The R ｂ are each independently deuterium or substituted with at least one deuterium; The R ｅ and the R ｆ 3. The semiconductor photoresist composition according to claim 2, wherein at least one of is deuterium or is substituted with at least one deuterium.

5. The R ａ and the R ｊ each independently represents a methyl group substituted with at least one deuterium, an ethyl group substituted with at least one deuterium, a propyl group substituted with at least one deuterium, a butyl group substituted with at least one deuterium, an isopropyl group substituted with at least one deuterium, a tert-butyl group substituted with at least one deuterium, a tert-pentyl group substituted with at least one deuterium, a 2,2-dimethylpropyl group substituted with at least one deuterium, a cyclopropyl group substituted with at least one deuterium, a cyclobutyl ... a cyclopentyl group, a cyclohexyl group substituted with at least one deuterium, an ethenyl group substituted with at least one deuterium, a propenyl group substituted with at least one deuterium, a butenyl group substituted with at least one deuterium, an ethynyl group substituted with at least one deuterium, a propynyl group substituted with at least one deuterium, a butynyl group substituted with at least one deuterium, a phenyl group substituted with at least one deuterium, a tolyl group substituted with at least one deuterium, a xylene group substituted with at least one deuterium, a benzyl group substituted with at least one deuterium, or a combination thereof; The R ｂ and the R ｋ are each independently deuterium, a methyl group substituted with at least one deuterium, an ethyl group substituted with at least one deuterium, a propyl group substituted with at least one deuterium, a butyl group substituted with at least one deuterium, an isopropyl group substituted with at least one deuterium, a tert-butyl group substituted with at least one deuterium, a tert-pentyl group substituted with at least one deuterium, a 2,2-dimethylpropyl group substituted with at least one deuterium, a cyclopropyl group substituted with at least one deuterium, a cyclobutyl group substituted with at least one deuterium, a cyclopentyl group, a cyclohexyl group substituted with at least one deuterium, an ethenyl group substituted with at least one deuterium, a propenyl group substituted with at least one deuterium, a butenyl group substituted with at least one deuterium, an ethynyl group substituted with at least one deuterium, a propynyl group substituted with at least one deuterium, a butynyl group substituted with at least one deuterium, a phenyl group substituted with at least one deuterium, a tolyl group substituted with at least one deuterium, a xylene group substituted with at least one deuterium, a benzyl group substituted with at least one deuterium, or a combination thereof; The R ｃ , the R ｄ , the R ｅ , the R ｆ , the R ｇ , the R ｈ and the R ｉ are each independently hydrogen, deuterium, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted tert-pentyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted ethenyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butenyl group, a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propynyl group, a substituted or unsubstituted butynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted xylene group, a substituted or unsubstituted benzyl group, or a combination thereof; The R ｃ and the R ｄ at least one of the R ｅ and the R ｆ and at least one of the R ｇ , the R ｈ and the R ｉ at least one of which is independently selected from the group consisting of deuterium, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, tert-pentyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, and cyclopentyl groups.

4. The semiconductor photoresist composition according to claim 3, wherein the substituted or unsubstituted alkyl group is selected from the group consisting of an alkyl group, an alkyl aryl group, an alkyl cyclohexyl group substituted with at least one deuterium, an aryl ...

6. 2. The semiconductor photoresist composition according to claim 1, wherein the deuterium substitution rate of the hydrolyzable ligand is 1 to 100%.

7. 2. The semiconductor photoresist composition according to claim 1, wherein the hydrolyzable ligand is derived from propionic acid, 4-methyl-2-pentanol (MIBC), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), furoic acid, diethylamine, or methyl isobutyrate.

8. 2. The semiconductor photoresist composition according to claim 1, wherein the organotin compound is contained in an amount of 0.5 to 30% by weight based on 100% by weight of the semiconductor photoresist composition.

9. 10. The semiconductor photoresist composition of claim 1, further comprising an additive selected from the group consisting of a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, and combinations thereof.

10. forming a film to be etched on a substrate; applying the semiconductor photoresist composition according to any one of claims 1 to 9 onto the film to be etched, and heating the composition at a temperature of 110°C to 180°C to form a photoresist film; exposing and developing the photoresist film to form a photoresist film having a photoresist pattern formed thereon; and etching the target layer using the photoresist pattern as an etching mask.

11. The root mean square roughness (R ｑ 11. The pattern formation method according to claim 10, wherein the root mean square roughness is less than 0.

4.

12. 11. The pattern formation method according to claim 10, wherein the photoresist film contains Sn--O--Sn and Sn--O--D bonds.

13. 11. The pattern formation method according to claim 10, wherein after exposure, the photoresist pattern contains Sn--O--Sn and Sn--O--D bonds.

Images