Composition for semiconductor photoresist, and method for forming patterns using the same

Abstract

This invention provides a semiconductor photoresist composition that enables the realization of photoresist patterns with improved moisture stability, coating properties, and LER characteristics, as well as a pattern formation method utilizing the same. [Solution] The present invention relates to a semiconductor photoresist composition comprising an organometallic compound represented by chemical formula 1 and a solvent, and a pattern formation method utilizing the same. Details regarding Chemical Formula 1 are as described in the specification.

Description

[Technical Field]

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

[0002] EUV (extreme ultraviolet) lithography is attracting attention as one of the key technologies for manufacturing next-generation semiconductor devices. EUV lithography is a pattern formation technique that uses EUV light with a wavelength of 13.5 nm as the exposure light source. EUV lithography has been demonstrated to be able to form extremely fine patterns (for example, less than 20 nm) in the exposure process of semiconductor device manufacturing.

[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 striving to meet the specifications for resolution, photospeed, feature roughness, and line edge roughness (LER) for next-generation devices.

[0004] The intrinsic image blur caused by acid-catalyzed reactions in these polymer-type photoresists limits resolution at small feature sizes, a fact long known in electron beam lithography. Chemically amplified (CA) photoresists, while designed for high sensitivity, can sometimes experience further difficulties, partly under EUV exposure, because their typical elemental makeup reduces the photoresist absorbance at a wavelength of 13.5 nm, thereby decreasing sensitivity.

[0005] CA photoresists also sometimes experience difficulties due to roughness issues with small feature sizes, and experiments have shown that line edge roughness (LER) increases due to a decrease in photospeed, partly due to the nature of the acid-catalyzed process. Due to the shortcomings and problems of CA photoresists, the semiconductor industry has a demand 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. Inorganic photosensitive compositions are mainly used for negative tone patterning, where chemical modification by non-chemical amplification mechanisms results in resistance to removal by developer compositions. Inorganic compositions contain inorganic elements that have a higher EUV absorption rate compared to hydrocarbons, ensuring sensitivity even with non-chemical amplification mechanisms, and are less sensitive to the stochastic effect, resulting in fewer line edge roughness and defects.

[0007] Inorganic photoresists based on tungsten and peroxopolyacids of tungsten mixed with niobium, titanium, and / or tantalum have been reported for 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 and have been effective in patterning large features in bilayer configurations. More recently, impressive performance has been demonstrated when using cationic hafnium metal oxide sulfate (HfSOx) materials with a peroxo complexing agent to image a 15 nm half-pitch (HP) by projection EUV lithography (US2011-0045406; JKStowers, A.Telecky, M.Kocsis, BLClark, DAKeszler, A.Grenville, CNAnderson, PPNaulleau, Proc.SPIE, 7969, 796915, 2011). This system exhibits the best performance of non-CA photoresists and has a light speed that approaches the requirements for a viable EUV photoresist. However, hafnium metal oxide sulfate materials containing peroxo-complexing agents have several practical drawbacks. Firstly, these materials are coated with a highly corrosive sulfuric acid / hydrogen peroxide mixture, resulting in poor shelf-life stability. Secondly, they are complex mixtures, making structural modifications for performance improvement difficult. Thirdly, they must be developed with extremely high concentrations of TMAH (tetramethylammonium hydroxide) solution, such as 25 wt%, or similar.

[0009] Recently, with the discovery that molecules containing tin exhibit excellent extreme ultraviolet absorption, active research has been conducted. In the case of organotin polymers, one of them, negative tone patterning that cannot be removed by an organic developer through crosslinking by oxo bonds with peripheral chains while the alkyl ligand dissociates due to 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, but additional improvement of the patterning characteristics is required for commercialization.

Summary of the Invention

Problems to be Solved by the Invention

[0010] One embodiment of the present invention provides a composition for a semiconductor photoresist that can realize a photoresist pattern with improved moisture stability, coating properties, and LER characteristics.

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

Means for Solving the Problems

[0012] The composition for a semiconductor photoresist according to one embodiment of the present invention contains an organometallic compound represented by the following Chemical Formula 1 and a solvent.

[0013]

Chem.

[0014] In Chemical Formula 1, R 1This is selected from substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C2-C30 heteroalkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C30 heterocycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C2-C30 heteroaryl groups, substituted or unsubstituted C7-C30 arylalkyl groups, substituted or unsubstituted C4-C30 heteroarylalkyl groups, and substituted or unsubstituted C1-C30 alkylcarbonyl groups. X, Y, and Z are each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C30 heteroalkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C30 heterocycloalkyl 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 C2-C30 heteroaryl group, a substituted or unsubstituted C7-C30 arylalkyl group, a substituted or unsubstituted C4-C30 heteroarylalkyl group, a substituted or unsubstituted C1-C30 alkylcarbonyl group, an alkoxy, and an aryloxy (-OR) a , here R a (which 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 bis hydrogen, 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), -O-L 1 -S-R 2 and -O(CO)-L 2 -S-R 3 is selected from among At least one of X, Y, and Z is -O-L 1 -S-R 2 and -O(CO)-L 2 -S-R 3 is selected from among Said L 1 and L 2 are each independently a single bond or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, Said R 2 and R 3 are each independently 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.

[0015] A pattern formation method according to another embodiment of the present invention includes a step of forming an etching target film on a substrate, a step of applying the above-described composition for a semiconductor photoresist on the etching target film to form a photoresist film, a step of exposing and developing the photoresist film to form a photoresist film having a photoresist pattern formed thereon, and a step of etching the etching target film using the photoresist pattern as an etching mask.

Advantages of the Invention

[0016] A semiconductor photoresist composition according to one embodiment of the present invention has improved storage stability, thereby providing a photoresist pattern with improved sensitivity and LER characteristics. [Brief explanation of the drawing]

[0017] [Figure 1] This is a cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment. [Modes for carrying out the invention]

[0018] Embodiments of the present invention will be described in detail below with reference to the attached drawings. However, in order to clarify the gist of this description, explanations of functions or configurations that are already publicly known will be omitted.

[0019] To clearly explain this description, unnecessary explanatory parts have been omitted, and the same or similar components are denoted by the same reference numerals throughout the specification. Furthermore, the dimensions and thicknesses of each component shown in the drawings are arbitrarily shown for explanatory purposes, and this description is not necessarily limited to those shown.

[0020] In the drawings, the thicknesses were enlarged to clearly represent multiple layers and regions. Furthermore, for explanatory purposes, the thicknesses of some layers and regions were exaggerated in the drawings. When a layer, film, region, plate, or other part is said to be "on top of" another part, this includes not only cases where it is "directly on top" of another part, but also cases where there is another part in between.

[0021] In this document, "substituted" means that the hydrogen atom is replaced by deuterium, halogen group, hydroxyl group, carboxyl group, thiol group, cyano group, nitro group, -NRR' (where R and R' are 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'' (where R, R', and R'' are independently hydrogen, a substituted or unsubstituted This means that the group is substituted with an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, or a combination thereof. "Unsubstituted" means that the hydrogen atom is not substituted by another substituent and remains as a hydrogen atom.

[0022] In this specification, "alkyl (alkyl) group" means a linear or branched aliphatic hydrocarbon group unless otherwise defined. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0023] 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, or a tert-butyl group or a 2,2-dimethylpropyl group.

[0024] In this document, "cycloalkyl group" refers to a monovalent cyclic aliphatic saturated hydrocarbon group unless otherwise defined.

[0025] 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.

[0026] In this specification, “aliphatic unsaturated organic group” means a hydrocarbon group that contains a bond between carbon atoms in the molecule that is a double bond, a triple bond, or a combination thereof.

[0027] 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, an 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.

[0028] In this specification, “aryl group” means a substituent in which all elements of the cyclic substituent have p-orbitals and these p-orbitals form a conjugation, and includes monocyclic or fused-ring polycyclic (i.e., rings sharing adjacent pairs of carbon atoms) functional groups.

[0029] In this specification, a "heteroaryl group" means 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 can be directly linked through sigma bonds, or, if the heteroaryl group contains two or more rings, the two or more rings can be fused together. If the heteroaryl group is a fused ring, each ring may contain one to three of the heteroatoms.

[0030] In this specification, "alkenyl group" means an aliphatic unsaturated alkenyl group, which is a linear or branched aliphatic hydrocarbon group containing one or more double bonds, unless otherwise defined.

[0031] In this specification, "alkynyl group" means an aliphatic unsaturated alkynyl group, which is a linear or branched aliphatic hydrocarbon group containing one or more triple bonds, unless otherwise defined.

[0032] A semiconductor photoresist composition according to one embodiment will be described below.

[0033] A semiconductor photoresist composition according to one embodiment of the present invention may contain an organometallic compound represented by the following chemical formula 1 and a solvent.

[0034] [ka]

[0035] In the above chemical formula 1, R 1This is selected from substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C2-C30 heteroalkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C30 heterocycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C2-C30 heteroaryl groups, substituted or unsubstituted C7-C30 arylalkyl groups, substituted or unsubstituted C4-C30 heteroarylalkyl groups, and substituted or unsubstituted C1-C30 alkylcarbonyl groups. X, Y, and Z are each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C30 heteroalkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C30 heterocycloalkyl 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 C2-C30 heteroaryl group, a substituted or unsubstituted C7-C30 arylalkyl group, a substituted or unsubstituted C4-C30 heteroarylalkyl group, a substituted or unsubstituted C1-C30 alkylcarbonyl group, an alkoxy, and an aryloxy (-OR) a , here R a (which 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(where 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), -OL 1 -SR 2 and -O(CO)-L 2 -SR 3 Selected from among, At least one of X, Y, and Z is -OL 1 -SR 2 and -O(CO)-L 2 -SR 3 Selected from among, Said L 1 and L 2 Each of these is independently a single-bonded, substituted, or unsubstituted alkylene group having 1 to 10 carbon atoms. The aforementioned R 2 and R 3 Each of these is independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof.

[0036] The organometallic compounds according to the present invention, by substituting a hydrolyzable alkoxy group or carboxyl group with a heteroatom S having high electronegativity, possess abundant electron density in a neutral state and can function as ligands that coordinate to metals and metal cations.

[0037] Since the ligand containing the heteroatom S has excellent binding affinity to metals, it promotes the elimination reaction of hydrocarbyl groups in the exposed area, inducing the metal cation to exist as a mononuclear complex. This reduces the degree of crosslinking in the unexposed area, thereby further improving sensitivity and LER characteristics.

[0038] As an example, X, Y, and Z are each independent of -OL 1 -SR 2 and -O(CO)-L 2 -SR 3 You can choose from the following options.

[0039] For example, X, Y, and Z may be the same as each other.

[0040] As an example, R 1 The group can be selected from substituted or unsubstituted C1-C10 alkyl groups, substituted or unsubstituted C2-C20 heteroalkyl groups, substituted or unsubstituted C3-C12 cycloalkyl groups, substituted or unsubstituted C2-C20 heterocycloalkyl groups, substituted or unsubstituted C2-C10 alkenyl groups, substituted or unsubstituted C2-C10 alkynyl groups, substituted or unsubstituted C6-C20 aryl groups, substituted or unsubstituted C2-C20 heteroaryl groups, substituted or unsubstituted C7-C20 arylalkyl groups, substituted or unsubstituted C4-C20 heteroarylalkyl groups, and substituted or unsubstituted C1-C20 alkylcarbonyl groups.

[0041] As a specific example, R 1This group may be 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 1-methylpropyl group, a substituted or unsubstituted 1,1-dimethylpropyl 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.

[0042] For example, the R 2 and R 3 Each of these can independently be a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

[0043] In one embodiment, the R 2 and R 3 Each of these can independently be a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0044] In one specific embodiment, the organometallic compound represented by chemical formula 1 can be selected from the compounds listed in Group 1 below.

[0045] [ka]

[0046] The organometallic compound represented by chemical formula 1 strongly absorbs extreme ultraviolet light at 13.5 nm and exhibits excellent sensitivity to high-energy light.

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

[0048] A semiconductor photoresist composition according to one embodiment of the present invention, by containing the above-mentioned organometallic compound, can provide a semiconductor photoresist composition having excellent sensitivity and pattern-forming properties.

[0049] The solvent contained in the semiconductor photoresist composition according to one embodiment may be an organic solvent, and may include, but is 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 contain a resin in addition to the organometallic compound and the solvent.

[0051] The aforementioned resin may be a phenolic resin containing at least one of the aromatic molecules 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 included in an amount of 0.1% to 50% by weight relative to the total content of the semiconductor photoresist composition.

[0055] When the aforementioned resin is included within the above-mentioned content range, it can have excellent etching resistance and heat resistance.

[0056] On the other hand, a semiconductor photoresist composition according to one embodiment is preferably composed of the organometallic compound, solvent, and resin described above. However, the semiconductor photoresist composition according to the above embodiment may optionally further contain additives. Examples of such additives include surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0057] The surfactant may be, but is not limited to, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts, or combinations 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, or polymer-based crosslinking agents. Examples of crosslinking agents having at least two crosslinking substituents include compounds such as methoxymethylated glycolyl, butoxymethylated glycolyl, 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-cyclohexane dicarboxylate, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea.

[0059] Leveling agents are used to improve coating flatness during printing, and commercially available, known leveling agents can be used.

[0060] Organic acids may include, but are 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 may 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 according to the desired physical properties, and they can also be omitted.

[0063] Furthermore, the semiconductor photoresist composition may be further enhanced with a silane coupling agent as an adhesion enhancer to improve adhesion to the substrate (for example, to improve the adhesion strength of the semiconductor photoresist composition to the substrate). The silane coupling agent may be, but is not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; or carbon-carbon unsaturated bond-containing silane compounds such as trimethoxy[3-(phenylamino)propyl]silane.

[0064] The semiconductor photoresist composition may not experience pattern collapse even when forming patterns with a high aspect ratio. Therefore, it can be used in photoresist processes using light with wavelengths of 5 nm to 150 nm, such as a photoresist process using light with wavelengths of 5 nm to 100 nm, such as a photoresist process using light with wavelengths of 5 nm to 100 nm, such as a photoresist process using light with wavelengths of 5 nm to 80 nm, such as a photoresist process using light with wavelengths of 5 nm to 50 nm, such as a photoresist process using light with wavelengths of 5 nm to 30 nm, such as a photoresist process using light with wavelengths of 5 nm to 20 nm, for example, to form fine patterns with widths of 5 nm to 100 nm, such as a photoresist process using light with wavelengths of 5 nm to 830 nm, and such as a photoresist process using light with wavelengths of 5 nm to 20 nm. Therefore, by using a semiconductor photoresist composition according to one embodiment, extreme ultraviolet lithography using an EUV light source with a wavelength of approximately 13.5 nm can be realized.

[0065] On the other hand, according to another embodiment, a method for forming a pattern using the semiconductor photoresist composition can be provided. For example, the manufactured pattern may be a photoresist pattern.

[0066] A pattern formation method according to one embodiment includes the steps of: forming an etching target film on a substrate; applying the semiconductor photoresist composition on the etching target film to form a photoresist film; exposing and developing the photoresist film to form a photoresist film on which a photoresist pattern is formed; and etching the etching target film using the photoresist pattern as an etching mask.

[0067] The following describes a method for forming a pattern using the semiconductor photoresist composition described above, with reference to Figure 1. Figure 1 is a cross-sectional view illustrating a pattern formation method using the semiconductor photoresist composition according to the present invention.

[0068] Referring to Figure 1(a), first, the object to be etched is prepared. An example of the object to be etched is a thin film 102 formed on a semiconductor substrate 100. The following explanation will only cover the case where the object to be etched is a thin film 102. The surface of the thin film 102 is cleaned to remove any 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 resist underlayer forming composition for forming a resist underlayer 104 is coated onto the surface of the cleaned thin film 102 using a spin coating method. However, one embodiment is not necessarily 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, can also be used.

[0070] The above-mentioned resist underlayer coating step can be omitted, and the following description will focus on the case where the resist underlayer is coated.

[0071] Subsequently, a drying and baking process is performed to form a resist underlayer film 104 on the thin film 102. The baking process is carried out at approximately 100 to 500°C, for example, at approximately 100°C to 300°C.

[0072] The resist underlayer 104 is formed between the substrate 100 and the photoresist film 106. This prevents the scattering of irradiation lines reflected from the interface between the substrate 100 and the photoresist film 106 or from the interlayer hard mask into unintended photoresist regions, thereby preventing non-uniformity of the photoresist linewidth and interference with pattern formation.

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

[0074] More specifically, the step of forming a pattern using a semiconductor photoresist composition may include the steps of applying the semiconductor photoresist composition onto a substrate 100 on which a thin film 102 is formed by spin coating, slit coating, inkjet printing, etc., and drying the applied semiconductor photoresist composition to form a photoresist film 106.

[0075] Since the compositions for semiconductor photoresists have already been explained in detail, we will omit further explanation.

[0076] Next, a first baking step is performed in which the substrate 100 on which the photoresist film 106 is formed is heated. The first baking step can be performed at a temperature of approximately 80°C to approximately 120°C.

[0077] Referring to Figure 1(c), the photoresist film 106 is selectively exposed using a patterned mask 110.

[0078] As an example, examples of light that can be used in the exposure process include not only short-wavelength light such as the activation irradiation diagram i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), but also high-energy wavelength light such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0079] More specifically, the exposure light according to one embodiment may be short-wavelength light having a wavelength range of 5 nm to 150 nm, and may be light having a high-energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0080] The exposed region 106b in the photoresist film 106 forms a polymer through crosslinking reactions such as condensation between organometallic compounds, resulting in a solubility different from that of the unexposed region 106a of the photoresist film 106.

[0081] Next, a second baking step is performed on the substrate 100. The second baking step can be performed at a temperature of approximately 90°C to approximately 200°C. By performing the second baking step, the exposed region 106b of the photoresist film 106 becomes less soluble in the developer.

[0082] Figure 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 pattern 108 corresponding to the negative tone image is completed by dissolving and then removing the photoresist film 106a corresponding to the unexposed region using an organic solvent such as 2-heptanone.

[0083] As described above, the developer used in the pattern formation method according to one embodiment may be an organic solvent. Examples of organic solvents used in the pattern formation method according to one 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.

[0084] However, the photoresist pattern according to one embodiment is not necessarily limited to being formed as a negative tone image, but can also be formed to have a positive tone image. In this case, examples of 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.

[0085] As described above, the photoresist pattern 108 formed by exposure with light having wavelengths such as i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm), and ArF excimer laser (wavelength 193nm), as well as high-energy light such as EUV (Extreme UltraViolet; wavelength 13.5nm) and E-Beam (electron beam), can have a width of 5nm to 100nm in thickness. For example, the photoresist pattern 108 can be formed with widths of 5nm to 90nm, 5nm to 80nm, 5nm to 70nm, 5nm to 60nm, 5nm to 50nm, 5nm to 40nm, 5nm to 30nm, 5nm to 20nm, and 5nm to 10nm.

[0086] On the other hand, the photoresist pattern 108 can have a half-pitch of approximately 50 nm or less, for example 40 nm or less, for example 30 nm or less, for example 20 nm or less, for example 10 nm or less, and a pitch having a line width roughness of approximately 5 nm or less, approximately 3 nm or less, approximately 2 nm or less, or approximately 1 nm or less.

[0087] Furthermore, according to another embodiment, a photoresist film manufactured by the pattern forming method described above can be provided.

[0088] Next, the photoresist pattern 108 formed on the photoresist film is used as an etching mask to etch the resist underlayer film 104. This etching process forms an organic film pattern 112. The formed organic film pattern 112 can also have a width corresponding to the photoresist pattern 108.

[0089] Referring to Figure 1(e), the photoresist pattern 108 is applied as an etching mask to etch the exposed thin film 102. As a result, the thin film is formed as a thin film pattern 114.

[0090] The thin film 102 can be etched, for example, by dry etching using an etching gas, and the etching gas can be, for example, CHF3, CF4, Cl2, BCl3, or a mixture thereof.

[0091] The thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process using an EUV light source in the preceding exposure process can have a width corresponding to the photoresist pattern 108. For example, it can have a width of 5 nm to 100 nm, similar to the photoresist pattern 108. For instance, the thin film pattern 114 formed by the exposure process using an EUV light source can have widths 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, and 5 nm to 20 nm, similar to the photoresist pattern 108, and more specifically, it can be formed with a width of 20 nm or less. [Examples]

[0092] The present invention will be described in more detail below through the examples of the manufacturing of the semiconductor photoresist composition described above. However, the technical features of the present invention are not limited by the following examples.

[0093] (Synthesis of organometallic compounds) Synthesis Example 1 24.1 g of the organotin compound (t-BuSn(NEt2)3) represented by the following chemical formula A was dissolved in 200 mL of toluene and stirred at room temperature. The temperature of the solution was lowered to 0°C, and 18.7 g of 2-(methylthio)-ethanol was slowly added dropwise. The mixture was then heated to room temperature while stirring for 12 hours. After removing the volatile portion from the mixture under reduced pressure, the residual liquid was subjected to vacuum fractional distillation to obtain the organotin compound represented by the following chemical formula 2.

[0094] [ka]

[0095] [ka]

[0096] Synthesis Example 2 14.5 g of the organotin compound (t-BuSn(NEt2)3) represented by the above chemical formula A was dissolved in 150 mL of toluene and stirred at room temperature. The temperature of the solution was lowered to 0°C, and 13.0 g of 3-(methylthio)-1-propanol was slowly added dropwise. The mixture was then heated to room temperature while stirring for 12 hours. After removing the volatile portion from the mixture under reduced pressure, the residual liquid was subjected to vacuum fractional distillation to obtain the organotin compound represented by the following chemical formula 3.

[0097] [ka]

[0098] Synthesis Example 3 30.1 g of the organotin compound (t-BuSn(NEt2)3) represented by the above chemical formula A was dissolved in 250 mL of anhydrous toluene and stirred at room temperature. The temperature of the solution was lowered to 0°C, and 39.3 g of 2-thiophene carboxylic acid was slowly added dropwise. The mixture was then heated to room temperature while stirring for 4 hours. After removing the volatile portion from the mixture under reduced pressure, the residual liquid was subjected to vacuum fractional distillation to obtain the organotin compound represented by the following chemical formula 4.

[0099] [ka]

[0100] Comparative Synthesis Example 1 340.7g of t-butylSnPh and 300g of propionic acid were placed in a 250ml two-necked round-bottom flask and heated under reflux for 24 hours.

[0101] The unreacted propionic acid was removed under reduced pressure to obtain the compound represented by the following chemical formula 5.

[0102] [ka]

[0103] Comparative Synthesis Example 2 30 ml of anhydrous pentane was added to 10 g of t-AmylSnCl3, and the temperature was maintained at 0°C. Then, 7.4 g of diethylamine and 6.1 g of ethanol were added, and the mixture was stirred at room temperature for 1 hour. After the reaction was complete, the mixture was filtered, concentrated, and vacuum-dried to obtain the compound represented by the following chemical formula 6.

[0104] [ka]

[0105] Comparative Synthesis Example 3 Ten g of the organotin compound (t-BuSn(NEt2)3) represented by chemical formula A was dissolved in 30 mL of toluene, and then 8.2 g of 2-(methylthio)ethane-1-thiol was slowly added and the mixture was stirred at room temperature for 6 hours. Subsequently, the toluene and the separated diethylamine were removed by vacuum distillation to obtain the compound represented by chemical formula 7.

[0106] [ka]

[0107] (Manufacturing of semiconductor photoresist compositions) Examples 1-3 and Comparative Examples 1-3 The organometallic compounds obtained in Synthesis Examples 1-3 and Comparative Synthesis Examples 1-3 were each dissolved in 3 wt% PGMEA (propylene glycol monomethyl ether acetate), and the mixtures were filtered through a 0.1 μm PTFE syringe filter to produce photoresist compositions.

[0108] Evaluation 1: Sensitivity and Line Edge Roughness (LER) Evaluation The photoresist compositions according to the above examples and comparative examples were spin-coated onto a 200 mm circular silicon wafer whose surface was deposited with HMDS 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] Subsequently, a linear array of 50 circular pads with a diameter of 500 μm was projected onto a wafer coated with the photoresist composition using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). The pad exposure time was adjusted to ensure that the increasing EUV dose was applied to each pad.

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

[0111] The residual resist thickness of the exposed pads was measured using a polarization analysis method (Ellipsometer). The remaining thickness was measured for each exposure level, and the results were graphed as a function of the exposure level to determine the sensitivity. The LER was then measured from the FE-SEM images, and the results are shown in Table 1.

[0112] Evaluation 2: Storage stability evaluation The storage stability of the organometallic compounds used in Examples 1-3 and Comparative Examples 1-3 was evaluated according to the following criteria and is shown in Table 1 below.

[0113] [Storage stability] The semiconductor photoresist compositions prepared in Examples 1-3 and Comparative Examples 1-3 were left standing for a specified period under room temperature conditions. The degree of precipitation was observed visually and evaluated according to the following storage standards.

[0114] *Evaluation criteria -○: Can be stored for 3 months or more. -△: Can be stored for more than 1 week but less than 3 months. -X: Can be stored for less than one week.

[0115] Evaluation 3: Coating performance evaluation The photoresist compositions from Examples 1-3 and Comparative Examples 1-3 were spin-coated onto a wafer at 1500 rpm for 60 seconds, and then baked at 110°C for 60 seconds to form thin films. The surface roughness of the thin films was then measured using software (e.g., an optical profiler) from images taken with an atomic force microscope (AFM) according to the following criteria, and the results are shown in Table 1.

[0116] The mean square roughness (R) of surface roughness q ;root mean square roughness) refers to the root mean square (rms) of the vertical values ​​within the reference length of the roughness profile.

[0117] [Evaluation Criteria] -◎:Rq0.3nm or less -○: Rq more than 0.3nm and less than 0.4nm -X:Rq>0.4nm

[0118] [Table 1]

[0119] The results in Table 1 confirm that the patterns formed using the semiconductor photoresist compositions of Examples 1-3 exhibit superior sensitivity and storage stability, as well as significantly improved coating performance, while maintaining a comparable level of LER compared to Comparative Examples 1-3.

[0120] Although specific embodiments of the present invention have been described and illustrated above, it is obvious to those ordinary skill in the art that the present invention is not limited to the described embodiments and can be modified and transformed in various ways without departing from the spirit and scope of the invention. Therefore, such modifications or variations should not be understood individually from the technical spirit or viewpoint of the present invention, and the modified embodiments can be said to fall within the scope of the claims of the present invention. [Explanation of Symbols]

[0121] 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. Organometallic compounds represented by the following chemical formula 1; and Compositions for semiconductor photoresists containing a solvent: 【Chemistry 1】 In the aforementioned chemical formula 1, R １ This is selected from substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C2-C30 heteroalkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C30 heterocycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C2-C30 heteroaryl groups, substituted or unsubstituted C7-C30 arylalkyl groups, substituted or unsubstituted C4-C30 heteroarylalkyl groups, and substituted or unsubstituted C1-C30 alkylcarbonyl groups. X, Y, and Z are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 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, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 4 to 30 carbon atoms, a substituted or unsubstituted alkylcarbonyl group, an alkoxy, and an 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, 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), —O—L １ —S—R ２ and —O(CO)—L ２ —S—R ３ is selected from among, At least one of X, Y, and Z is -O-L １ -S-R ２ and -O(CO)-L ２ -S-R ３ Selected from among, Said L １ and L ２ Each of these is independently a single-bonded, substituted, or unsubstituted alkylene group having 1 to 10 carbon atoms. The aforementioned R ２ and R ３ Each of these is independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof.

2. The aforementioned X, Y, and Z are each independently -O-L １ -S-R ２ and -O(CO)-L ２ -S-R ３ A semiconductor photoresist composition according to claim 1, selected from among the following.

3. The semiconductor photoresist composition according to claim 2, wherein X, Y, and Z are the same as each other.

4. The aforementioned R １ The semiconductor photoresist composition according to claim 1, wherein is selected from substituted or unsubstituted C1-C10 alkyl groups, substituted or unsubstituted C2-C20 heteroalkyl groups, substituted or unsubstituted C3-C12 cycloalkyl groups, substituted or unsubstituted C2-C20 heterocycloalkyl groups, substituted or unsubstituted C2-C10 alkenyl groups, substituted or unsubstituted C2-C10 alkynyl groups, substituted or unsubstituted C6-C20 aryl groups, substituted or unsubstituted C2-C20 heteroaryl groups, substituted or unsubstituted C7-C20 arylalkyl groups, substituted or unsubstituted C4-C20 heteroarylalkyl groups, and substituted or unsubstituted C1-C20 alkylcarbonyl groups.

5. The aforementioned R １ substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted propyl group, substituted or unsubstituted butyl group, substituted or unsubstituted isopropyl group, substituted or unsubstituted tert-butyl group, substituted or unsubstituted tert-pentyl group, substituted or unsubstituted 1-methylpropyl group, substituted or unsubstituted 1,1-dimethylpropyl group, substituted or unsubstituted 2,2-dimethylpropyl group, substituted or unsubstituted cyclopropyl group, substituted or unsubstituted cyclobutyl group, substituted or The semiconductor photoresist composition according to claim 1, wherein is an 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.

6. The aforementioned R ２ and R ３ The semiconductor photoresist composition according to claim 1, wherein each of them is independently a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

7. The aforementioned R ２ and R ３ The semiconductor photoresist composition according to claim 1, wherein each of them is independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

8. The organometallic compound represented by chemical formula 1 is one selected from the compounds listed in Group 1 below, according to claim 1, for use in semiconductor photoresists: 【Chemistry 2】

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

10. The semiconductor photoresist composition according to claim 1, further comprising a surfactant, a crosslinking agent, a leveling agent, an organic acid, an inhibitor (quencher), or other additives in combination thereof.

11. The steps include forming an etching target film on a substrate, The steps include applying the semiconductor photoresist composition according to any one of claims 1 to 10 onto the etchable film to form a photoresist film, The steps include: exposing and developing the photoresist film to form a photoresist film on which a photoresist pattern is formed; A pattern formation method comprising the step of etching a film to be etched using the aforementioned photoresist pattern as an etching mask.

12. The pattern formation method according to claim 11, wherein the step of forming the photoresist pattern uses light with a wavelength of 5 nm to 150 nm.

13. The pattern forming method according to claim 11, wherein the photoresist pattern has a width of 5 nm to 100 nm.

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