Semiconductor photoresist composition and method of forming patterns using the same

Abstract

To provide a semiconductor photoresist composition having excellent sensitivity characteristics, and a method of forming patterns using the semiconductor photoresist composition.SOLUTION: The present invention relates to a semiconductor photoresist composition including: a Sn-containing organometallic compound; a compound represented by Chemical Formula 1; and a solvent, and a method of forming patterns using the semiconductor photoresist composition. The descriptions of Chemical Formula 1 are as detailed in the specification.SELECTED DRAWING: Figure 1

Description

Technical Field

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

Background Art

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

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

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

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

[0006] To overcome the shortcomings of the chemically amplified organic photosensitive compositions described above, inorganic photosensitive compositions have been studied. In the case of inorganic photosensitive compositions, they are mainly used for negative tone patterning that is resistant to removal by developer compositions through chemical modification by a non-chemically amplified mechanism. In the case of inorganic compositions, since they contain inorganic elements with a high EUV absorption rate compared to hydrocarbons, sensitivity can be ensured even with a non-chemically amplified mechanism, and they are said to be less sensitive to the stochastic effect, resulting in less 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 use as radiation sensitive materials for patterning (US5061599; H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298 - 300, 1986).

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

[0009] In recent years, molecules containing tin are known to have excellent extreme ultraviolet absorption and are being actively studied. In the case of an organotin polymer, any of them, the alkyl ligand dissociates due to light absorption or secondary electrons generated thereby, and negative tone patterning that cannot be removed by an organic developing solution is possible by crosslinking with an oxo bond to the peripheral chain. Such an organotin polymer has shown a dramatic improvement in sensitivity while maintaining resolution and line edge roughness, but further improvement in the patterning characteristics is required for commercialization.

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] One embodiment provides a composition for a semiconductor photoresist having excellent sensitivity characteristics.

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

[0012] The composition for a semiconductor photoresist according to one embodiment includes a Sn-containing organometallic compound; a compound represented by the following Chemical Formula 1, and a solvent.

CHEM.

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

[0014] The composition for semiconductor photoresist according to one embodiment can achieve excellent sensitivity and LER characteristics.

Brief Description of the Drawings

[0015]

Figure 1

Embodiments for Carrying Out the Invention

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

[0017] In order to clearly explain this description, parts not related to the explanation are omitted, and the same reference numerals are given to the same or similar components throughout the specification. Also, the sizes and thicknesses of the respective configurations shown in the drawings are arbitrarily shown for convenience of explanation, and this description is not necessarily limited to what is shown in the drawings.

[0018] In the drawings, in order to clearly show a plurality of layers and regions, the thickness is enlarged. Also, in the drawings, for convenience of explanation, the thicknesses of some layers and regions are exaggerated. When a part such as a layer, film, region, or plate is “on” or “above” another part, this includes not only the case where it is directly above the other part but also the case where there is another part in between.

[0019] From this description, "substitution" means that a hydrogen atom is deuterium, a halogen group, a hydroxy group, a thiol group, a cyano group, a nitro group, -NRR' (where R and R' are each independently hydrogen, a substituted or unsubstituted C1-C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3-C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6-C30 aromatic hydrocarbon group), -SiRR'R" (where R, R', and R" are each independently hydrogen, a substituted or unsubstituted C1-C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3-C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6-C30 aromatic hydrocarbon group), a C1-C30 alkyl group, a C1-C10 haloalkyl group, a C1-C10 alkylsilyl group, a C3-C30 cycloalkyl group, a C6-C30 aryl group, a C1-C20 alkoxy group, a C1-C20 sulfide group, or a combination thereof. "Unsubstituted" means that the hydrogen atom is not substituted by another substituent and remains a hydrogen atom.

[0020] In this specification, the term "alkyl group" means a linear or branched aliphatic hydrocarbon group, unless otherwise defined. The alkyl group may be a "saturated alkyl group" having no double or triple bonds.

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

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

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

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

[0025] The aliphatic unsaturated organic group may be a C2-C8 aliphatic unsaturated organic group. For example, the aliphatic unsaturated organic group may be a C2-C7 aliphatic unsaturated organic group, a C2-C6 aliphatic unsaturated organic group, a C2-C5 aliphatic unsaturated organic group, or a C2-C4 aliphatic unsaturated organic group. For example, the C2-C4 aliphatic unsaturated organic group may be a vinyl group, an ethynyl group, an aryl 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 "aryl group" means a substituent in which all elements of the cyclic substituent have p-orbitals and these p-orbitals form conjugation, and includes monocyclic or fused-ring polycyclic (i.e., rings sharing adjacent pairs of carbon atoms) functional groups.

[0027] As used herein, the term "heteroaryl group" means that the aryl group contains 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 via a sigma bond, or when the heteroaryl group contains two or more rings, the two or more rings can be fused to each other. When the heteroaryl group is a fused ring, each ring can contain 1 to 3 of the heteroatoms.

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

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

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

[0031] A composition for a semiconductor photoresist according to an embodiment of the present invention can include a Sn-containing organometallic compound, a compound represented by the following Chemical Formula 1, and a solvent. [Chemical Formula] In Chemical Formula 1, R 1is an unsubstituted C3-C10 alkylene group, a substituted C1-C10 alkylene group, a substituted or unsubstituted C4-C20 cycloalkylene group, a substituted or unsubstituted C4-C20 cycloalkenylene group, a substituted or unsubstituted C3-C5 alkenylene group, a substituted or unsubstituted C3-C5 alkynylene group, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C2-C30 heterocycloalkylene group, a substituted or unsubstituted C2-C30 heteroarylene group, or a combination thereof.

[0032] The composition for a semiconductor photoresist contains a dicarboxyl compound, thereby increasing the sensitivity to extreme ultraviolet rays and being excellent in stability against line edge roughness (LER) and process delay.

[0033] In particular, when R in Chemical Formula 1 1 is cyclic and the total number of carbon atoms contained in the compound is 4 or more and 8 or less, the above-described effects are achieved. When R in Chemical Formula 1 1 is chain-like and the total number of carbon atoms contained in the compound is 3 or more, the above-described effects are achieved.

[0034] R 1 is chain-like, when the total number of carbon atoms contained in the compound is less than 3, the effect of improving stability decreases. When it exceeds 10, scum after development in the non-exposed part increases and the process margin decreases.

[0035] The above R 1is, for example, a divalent linking group derived from substituted methane, substituted ethane, substituted or unsubstituted propane, substituted or unsubstituted butane, substituted or unsubstituted pentane, substituted or unsubstituted cyclopentane, substituted or unsubstituted cyclopentene, substituted or unsubstituted cyclohexane, substituted or unsubstituted tetrahydropyran, substituted or unsubstituted 1,4-dioxane, substituted or unsubstituted tetrahydrothiopyran, substituted or unsubstituted 1,4-oxathiane, substituted or unsubstituted 1,4-dithiane, substituted or unsubstituted tetrahydrothiophene, substituted or unsubstituted dihydrothiophene, substituted or unsubstituted thiophene, substituted or unsubstituted tetrahydrofuran, substituted or unsubstituted dihydrofuran, substituted or unsubstituted furan, substituted or unsubstituted oxazolidine, substituted or unsubstituted oxazole, substituted or unsubstituted oxazoline, substituted or unsubstituted pyrrolidine, substituted or unsubstituted pyrroline, substituted or unsubstituted pyrrole, substituted or unsubstituted imidazolidine, substituted or unsubstituted imidazoline, substituted or unsubstituted imidazole, substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazoline, substituted or unsubstituted pyrazolidine, substituted or unsubstituted piperidine, substituted or unsubstituted morpholine, substituted or unsubstituted piperazine, substituted or unsubstituted pyridine, substituted or unsubstituted oxazine, or substituted or unsubstituted pyrazine.

[0036] As a specific example, the compound represented by the chemical formula 1 may be any of the compounds arranged in the following Group 1.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0037] The compound represented by the chemical formula 1 is contained in an amount of 0.01 to 10% by weight based on 100% by weight of the composition for semiconductor photoresist.

[0038] For example, the compound represented by the chemical formula 1 is contained in an amount of 0.01 to 5% by weight or 0.05 to 5% by weight based on 100% by weight of the composition for semiconductor photoresist.

[0039] The Sn-containing organometallic compound is contained in an amount of 0.5% to 30% by weight based on 100% by weight of the composition for semiconductor photoresist.

[0040] By including the Sn-containing organometallic compound and the compound represented by the chemical formula 1 within the above content ranges in the composition for semiconductor photoresist according to one embodiment, the sensitivity of the photoresist can be improved.

[0041] The composition for semiconductor photoresist according to one embodiment can contain the Sn-containing organometallic compound and the compound represented by the chemical formula 1 in a weight ratio of 99.9:0.1 to 80:20. For example, the semiconductor photoresist composition can contain the Sn-containing organometallic compound and the compound represented by the chemical formula 1 in a weight ratio of 95:5 to 85:15.

[0042] When the weight ratio of the Sn-containing organometallic compound and the compound represented by the chemical formula 1 satisfies the above range, a composition for semiconductor photoresist having excellent sensitivity can be provided.

[0043] The Sn-containing organometallic compound can contain at least one of an organic oxy group and an organic carbonyloxy group.

[0044] The Sn-containing organometallic compound is represented by the following chemical formula 2. [Chemical formula] In the above Chemical formula 2, R 2 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, a substituted or unsubstituted C6-C30 arylalkyl group, and L a -O-R a (where L a is a substituted or unsubstituted C1-C20 alkylene group, and R a is a substituted or unsubstituted C1-C20 alkyl group), and is selected from R 3 ~R 5 are each 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, a substituted or unsubstituted C6-C30 arylalkyl group, -OR b or -OC(=O)R c and R 3 ~R 5 at least one of which is selected from -OR b and -OC(=O)R c and R b is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof, R c 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.

[0045] On the one hand, the compound represented by the chemical formula 2 contains, as a ligand, -OR b or -OC(=O)R c By including this, the pattern formed using the semiconductor photoresist composition containing this exhibits excellent resolution limit.

[0046] Also, the ligand of -OR b or -OC(=O)R c can determine the solubility of the compound represented by the chemical formula 2 in the solvent.

[0047] The R 2 is a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C4-C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof, R b is a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof, R c may be hydrogen, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

[0048] The R 2is a methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylyl group, benzyl group, formyl group, acetyl group, propanoyl group, butanoyl group, pentanoyl group, ethoxy group, propoxy group, or a combination thereof, R b is an ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylyl group, benzyl group or a combination thereof, R c is hydrogen, an ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylyl group, benzyl group or a combination thereof.

[0049] In addition, the Sn-containing organometallic compound is represented by the following Chemical Formula 3 or Chemical Formula 4.

Chemical Formula

Chemical Formula

[0050] The solvent contained in the semiconductor photoresist composition according to one embodiment may be an organic solvent. As an example, it may include aromatic compounds (e.g., xylene, toluene), alcohols (e.g., 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropyl alcohol, 1-propanol), ethers (e.g., anisole, tetrahydrofuran), esters (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate), ketones (e.g., methyl ethyl ketone, 2-heptanone), mixtures thereof, etc., but is not limited thereto.

[0051] According to one embodiment, the composition for a semiconductor resist may further contain a resin in addition to the Sn-containing organometallic compound, the compound represented by Chemical Formula 1, and the solvent.

[0052] The resin may be a phenolic resin containing at least one aromatic moiety arranged in Group 2 below.

Chemical formula

[0053] The resin may be contained in an amount of 0.1% by weight to 50% by weight based on the total content of the composition for a semiconductor photoresist.

[0054] When the resin is contained within the above content range, it can have excellent etching resistance and heat resistance.

[0055] On the other hand, the composition for a semiconductor photoresist preferably consists of the above-described Sn-containing organometallic compound, the acid compound represented by Chemical Formula 1, the solvent, and the resin.

[0056] The composition for a semiconductor photoresist according to the above-described embodiments may optionally further contain an additive. Examples of the additive include a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, or a combination thereof.

[0057] As the surfactant, for example, an alkylbenzene sulfonate, an alkylpyridinium salt, polyethylene glycol, a quaternary ammonium salt, or a combination thereof can be used, but it is not limited thereto.

[0058] The crosslinking agent can be, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, an acrylic-based crosslinking agent, an epoxy-based crosslinking agent, or a polymer-based crosslinking agent, etc., but is not limited thereto. Examples of the crosslinking agent having at least two crosslinking-forming substituents include, for example, 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-cyclohexanedicarboxylate, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea and other compounds can be used.

[0059] The leveling agent is for improving the flatness of the coating during printing, and known leveling agents available by commercial methods can be used.

[0060] The organic acid may be p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, fluorinated sulfonate, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or a combination thereof, but is not limited thereto.

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

[0062] In one embodiment, an acid compound different from the compound represented by Chemical Formula 1 can be mixed in the composition for a semiconductor photoresist according to the present invention, and examples of the mixable acid compound include mono-acid.

[0063] The usage amounts of these additives can be easily adjusted according to desired physical properties and can also be omitted.

[0064] In addition, for the composition for a semiconductor photoresist, in order to improve the adhesion to a substrate (for example, in order to improve the adhesion between the composition for a semiconductor photoresist and the substrate), a silane coupling agent can be further used as an additive as an adhesion promoter. Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; carbon-carbon unsaturated bond-containing silane compounds such as trimethoxy[3-(phenylamino)propyl]silane, etc. can be used, but are not limited thereto.

[0065] The above-described semiconductor photoresist composition may not cause pattern collapse even when forming a pattern having a high aspect ratio. Therefore, for example, in order to form a fine pattern having a width of 5 nm to 100 nm, for example, a fine pattern having a width of 5 nm to 80 nm, for example, a fine pattern having a width of 5 nm to 70 nm, for example, a fine pattern having a width of 5 nm to 50 nm, for example, a fine pattern having a width of 5 nm to 40 nm, for example, a fine pattern having a width of 5 nm to 30 nm, for example, a fine pattern having a width of 5 nm to 20 nm, it can be used in a photoresist process using light having a wavelength of 5 nm to 150 nm, for example, a photoresist process using light having a wavelength of 5 nm to 100 nm, for example, a photoresist process using light having a wavelength of 5 nm to 80 nm, for example, a photoresist process using light having a wavelength of 5 nm to 50 nm, for example, a photoresist process using light having a wavelength of 5 nm to 30 nm, for example, a photoresist process using light having a wavelength of 5 to 20 nm. Therefore, by using the semiconductor photoresist composition according to an embodiment, extreme ultraviolet lithography using an EUV light source having a wavelength of about 13.5 nm can be realized.

[0066] On the other hand, according to another embodiment, a method of forming a pattern using the above-described semiconductor photoresist composition can be provided. As an example, the manufactured pattern may be a photoresist pattern.

[0067] Another pattern formation method according to an embodiment includes a step of forming an etching target film on a substrate, a step of applying the above-described semiconductor photoresist composition on the etching target film to form a photoresist film, a step of patterning the photoresist film to form a photoresist pattern, and a step of etching the etching target film using the photoresist pattern as an etching mask.

[0068] Hereinafter, a method for forming a pattern using the above-described composition for a semiconductor photoresist will be described with reference to FIG. 1. FIG. 1 is a cross-sectional view for explaining a pattern forming method using the composition for a semiconductor photoresist according to the present invention.

[0069] Referring to FIG. 1(a), a priority etching object is provided. As an example of the etching object, it can be a thin film 102 formed on a semiconductor substrate 100. Hereinafter, the description will be made only when the etching object 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 can be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film.

[0070] Subsequently, a composition for forming a resist underlayer film for forming a resist underlayer film 104 is spin-coated on the surface of the cleaned thin film 102. However, one embodiment is not necessarily limited to this, and various known coating methods, for example, spray coating, dip coating, knife edge coating, printing methods such as inkjet printing and screen printing, etc. can also be used.

[0071] The resist underlayer film coating process can be omitted, and hereinafter, the case of coating the resist underlayer film will be described.

[0072] Thereafter, a drying and baking process is performed to form a resist underlayer film 104 on the thin film 102. The baking treatment is performed at about 100 to about 500 °C, and for example, it can be performed at about 100 °C to about 300 °C.

[0073] The resist underlayer film 104 is formed between the substrate 100 and the photoresist film 106, and when the irradiated rays reflected from the substrate 100 or the interlayer hardmask are scattered into unintended photoresist regions, it can prevent non-uniformity of the photoresist linewidth and pattern formation ability.

[0074] Referring to FIG. 1(b), the above-described semiconductor photoresist composition is coated on the resist underlayer film 104 to form a photoresist film 106. The photoresist film 106 may be in a form cured through a heat treatment process after the above-described semiconductor photoresist composition is coated on the thin film 102 formed on the substrate 100.

[0075] More specifically, the step of forming a pattern using the semiconductor photoresist composition may include a process of spin-coating, slit-coating, inkjet printing, etc. the above-described semiconductor photoresist composition on the substrate 100 on which the thin film 102 is formed, and a process of drying the applied semiconductor photoresist composition to form the photoresist film 106.

[0076] Since the semiconductor photoresist composition has already been described in detail, redundant description will be omitted.

[0077] Subsequently, a first baking process of heating the substrate 100 on which the photoresist film 106 is formed is performed. The first baking process can be performed at a temperature of about 80°C to about 120°C.

[0078] Referring to FIG. 1(c), the photoresist film 106 is selectively exposed using the patterned mask 110.

[0079] As an example, examples of the light that can be used in the exposure process include not only light with short wavelengths such as activation irradiation i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), but also light with high energy wavelengths such as EUV (Extreme UltraViolet; wavelength 13.5 nm), E-Beam (electron beam), and the like.

[0080] More specifically, the exposure light according to one embodiment can also be short-wavelength light having a wavelength range of 5 nm to 150 nm, or can be light having a high energy wavelength such as EUV (Extreme Ultra Violet; wavelength 13.5 nm), E-Beam (electron beam), and the like.

[0081] In the exposed region 106b of the photoresist film 106, a polymer is formed by a crosslinking reaction such as condensation between organometallic compounds, so that it has a solubility different from that of the unexposed region 106b of the photoresist film 106.

[0082] Subsequently, 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 difficult to dissolve in the developer.

[0083] FIG. 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, after dissolving the photoresist film 106b corresponding to the unexposed region using an organic solvent such as 2-heptanone and then removing it, the photoresist pattern 108 corresponding to the negative tone image is completed.

[0084] As described above, the developer used in the pattern formation method according to one embodiment may be an organic solvent.

[0085] As an example of the organic solvent used in the pattern formation method according to an embodiment, ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, methanol, esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, aromatic compounds such as benzene, xylene, toluene, or combinations thereof can be mentioned.

[0086] However, the photoresist pattern according to an embodiment is not necessarily limited to being formed as a negative tone image, and it can also be formed to have a positive tone image.

[0087] In this case, as the developer that can be used for forming a positive tone image, quaternary ammonium hydroxide compositions such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof can be mentioned.

[0088] As described above, the photoresist pattern 108 formed by exposure with light having a wavelength such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), as well as light having high energy such as EUV (Extreme UltraViolet; wavelength 13.5 nm), E-Beam (electron beam), etc. can have a width with a thickness of 5 nm to 100 nm.

[0089] As an example, the photoresist pattern 108 can be formed with a width having a thickness 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.

[0090] On the one hand, the photoresist pattern 108 can have a half-pitch of about 50 nm or less, for example, 40 nm or less, for example, 30 nm or less, for example, 20 nm or less, for example, 15 nm or less, and a pitch with a line width roughness of about 10 nm or less, about 5 nm or less, about 3 nm or less, about 2 nm or less.

[0091] Subsequently, the resist underlayer film 104 is etched using the photoresist pattern 108 as an etching mask. An organic film pattern 112 is formed in such an etching process. The formed organic film pattern 112 can have a width corresponding to that of the photoresist pattern 108.

[0092] Referring to FIG. 1(e), the thin film 102 exposed by applying the photoresist pattern 108 as an etching mask is etched. As a result, the thin film is formed into a thin film pattern 114.

[0093] The etching of the thin film 102 can be performed, for example, by dry etching using an etching gas, and the etching gas can use, for example, CHF3, CF4, Cl2, BCl3, and a mixed gas thereof.

[0094] In the exposure process performed previously, the thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process using an EUV light source can have a width corresponding to that of the photoresist pattern 108. As an example, it can 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 can have a width of 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, 5 nm to 20 nm similar to the photoresist pattern 108, and more specifically, it can be formed with a width of 20 nm or less.

Example

[0095] Hereinafter, the present invention will be described in more detail through examples related to the production of the above-described semiconductor photoresist composition. However, the technical features of the present invention are not limited by the following examples.

[0096] Synthesis of organometallic compounds Synthesis Example 1 Put 40.7 g of t-butylSnPh3 and 300 g of propionic acid into a 250 ml two-necked round bottom flask and heat under reflux for 24 hours.

[0097] Remove unreacted propionic acid under reduced pressure to obtain a compound represented by the following Chemical Formula 5.

Chemical formula

[0098] Synthesis Example 2 Add 30 ml of anhydrous pentane to 10 g of t-AmylSnCl3, maintain the temperature at 0 °C, then add 7.4 g of diethylamine and 6.1 g of ethanol, and stir at room temperature for 1 hour.

[0099] After the reaction is completed, filter, concentrate, and vacuum dry to obtain a compound represented by the following Chemical Formula 6.

Chemical formula

[0100] Synthesis Example 3 Dissolve 10 g of Dibutyltin dichloride in 30 mL of ether, then add 70 mL of 1 M aqueous sodium hydroxide (NaOH) solution and stir for 1 hour.

[0101] After stirring, filter the resulting solid, wash it three times with 25 mL of deionized water, and then perform drying under reduced pressure at 100 °C to obtain an organometallic compound having a weight average molecular weight of 1,500 represented by the following Chemical Formula 7.

Chemical formula

[0102] (Manufacture of Composition for Semiconductor Photoresist) Examples 1 to 14 and Comparative Examples 1 to 4 The compounds represented by Chemical Formulas 5 to 7 obtained in Synthesis Examples 1 to 3 and the dicarboxylic acid compound were dissolved in a mixed solution of Propylene glycol methyl ether acetate (PGMEA) and Propylene glycol methyl ether (PGME) at a weight ratio of 7:3 at a concentration of 3 wt% in the weight ratios described in Table 1 below, and filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to produce a composition for semiconductor photoresist.

[0103]

Table 1

[0104] Evaluation 1: Sensitivity and Line Edge Roughness (LER) Evaluation The photoresist compositions according to the above Examples and Comparative Examples were spin-coated on a 200 mm circular silicon wafer with a surface vapor-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.

[0105] Thereafter, 50 circular pad linear arrays with a diameter of 500 μm were projected onto the wafer coated with the photoresist composition using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). The pad exposure time was adjusted so that an EUV increased dose was applied to each pad.

[0106] Thereafter, the resist and the substrate were post-exposure baked on a hot plate at 160°C for 120 seconds. The baked film was developed in a PGMEA solvent to form a negative tone image. Finally, the process was terminated by performing hot plate baking at 150°C for 2 minutes.

[0107] The residual resist thickness of the exposed pads was measured using an ellipsometer. For each exposure amount, the remaining thickness was measured and graphed as a function of the exposure amount to measure the sensitivity. After measuring the LER from the FE-SEM images, the sensitivity and line edge roughness were evaluated according to the following criteria, and the results are shown in Table 2.

[0108] [Sensitivity Evaluation Criteria] -A: Less than 16 mJ / cm 2 Less than -B: 16 mJ / cm or more 2 Or more

[0109] [LER Evaluation Criteria] -○: 2 nm or less, -△: More than 2 nm and 5 nm or less, -X: More than 5 nm

[0110] [Table 2]

[0111] From the results in Table 2, it can be confirmed that the patterns formed using the photoresist compositions for semiconductors according to Examples 1 to 14 exhibit excellent sensitivity and LER characteristics compared to Comparative Examples 1 to 4.

[0112] The specific embodiments of the present invention have been described and illustrated above. However, the present invention is not limited to the described embodiments, and it is obvious to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modified or variant examples should not be individually understood from the technical idea or perspective of the present invention, and the modified embodiments should be deemed to belong to the scope of the claims of the present invention.

Explanation of Reference Numerals

[0113] 100... substrate, 102... thin film, 104... underlayer resist film, 106... photoresist film, 106a... unexposed area, 106b... exposed area, 108... photoresist pattern, 112... organic film pattern, 110... patterned mask, 114... thin film pattern.

Claims

1. An organometallic compound containing Sn; A compound represented by the following Chemical Formula 1; and A composition for a semiconductor photoresist, comprising a solvent: 【Chemical 1】 In the Chemical Formula 1, R １ is an unsubstituted C3-C10 alkylene group, a substituted C1-C10 alkylene group, a substituted or unsubstituted C4-C20 cycloalkylene group, a substituted or unsubstituted C4-C20 cycloalkenylene group, a substituted or unsubstituted C3-C5 alkenylene group, a substituted or unsubstituted C3-C5 alkynylene group, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C2-C30 heterocycloalkylene group, a substituted or unsubstituted C2-C30 heteroarylene group, or a combination thereof.

2. Said R １ is a divalent linking group derived from a substituted methane, a substituted ethane, a substituted or unsubstituted propane, a substituted or unsubstituted butane, a substituted or unsubstituted pentane, a substituted or unsubstituted cyclopentane, a substituted or unsubstituted cyclopentene, a substituted or unsubstituted cyclohexane, a substituted or unsubstituted tetrahydropyran, a substituted or unsubstituted 1,4-dioxane, a substituted or unsubstituted tetrahydrothiopyran, a substituted or unsubstituted 1,4-oxathiane, a substituted or unsubstituted 1,4-dithiane, a substituted or unsubstituted tetrahydrothiophene, a substituted or unsubstituted dihydrothiophene, a substituted or unsubstituted thiophene, a substituted or unsubstituted tetrahydrofuran, a substituted or unsubstituted dihydrofuran, a substituted or unsubstituted furan, a substituted or unsubstituted oxazolidine, a substituted or unsubstituted oxazole, a substituted or unsubstituted oxazoline, a substituted or unsubstituted pyrrolidine, a substituted or unsubstituted pyrroline, a substituted or unsubstituted pyrrole, a substituted or unsubstituted imidazolidine, a substituted or unsubstituted imidazoline, a substituted or unsubstituted imidazole, a substituted or unsubstituted pyrazole, a substituted or unsubstituted pyrazoline, a substituted or unsubstituted pyrazolidine, a substituted or unsubstituted piperidine, a substituted or unsubstituted morpholine, a substituted or unsubstituted piperazine, a substituted or unsubstituted pyridine, a substituted or unsubstituted oxazine, or a substituted or unsubstituted pyrazine, the semiconductor photoresist composition according to claim 1.

3. The composition for a semiconductor photoresist according to Claim 1, wherein the compound represented by the Chemical Formula 1 is one of the compounds arranged in the following Group 1: 【Chemical Formula 2】 【Chemical Formula 3】 [Chemical Formula 4] [Chemical 5]

4. The composition for a semiconductor photoresist according to Claim 1, wherein the compound represented by the Chemical Formula 1 is glutaric acid, pimelic acid, methylsuccinic acid, phthalic acid, cyclohexanedicarboxylic acid, furandicarboxylic acid, or a combination thereof.

5. The composition for a semiconductor photoresist according to Claim 1, wherein the compound represented by the Chemical Formula 1 is contained in an amount of 0.01 to 10% by weight based on 100% by weight of the composition for a semiconductor photoresist.

6. The composition for a semiconductor photoresist according to Claim 1, wherein the compound represented by the Chemical Formula 1 is contained in an amount of 0.05 to 5% by weight based on 100% by weight of the composition for a semiconductor photoresist.

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

8. The composition for a semiconductor photoresist according to Claim 1, wherein the organometallic compound containing Sn and the compound represented by the Chemical Formula 1 are contained in a weight ratio of 99.9:0.1 to 80:

20.

9. The composition for a semiconductor photoresist according to Claim 1, further comprising an additive such as a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, or a combination thereof.

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

11. The composition for a semiconductor photoresist according to Claim 1, wherein the organometallic compound containing Sn is represented by the following Chemical Formula 2: 【Chemical Formula 6】 In the Chemical Formula 2, R ２ 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, a substituted or unsubstituted C6-C30 arylalkyl group, and L ａ -O-R ａ (wherein L ａ is a substituted or unsubstituted C1-C20 alkylene group and R ａ is a substituted or unsubstituted C1-C20 alkyl group) and is selected from R ３ to R ５ each independently represents a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 arylalkyl group, -OR ｂ or -OC(=O)R ｃ and R ３ to R ５ at least one of which is —OR ｂ and —OC(═O)R ｃ selected from, R ｂ is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof, R ｃ 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.

12. Said R ２ is a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C4-C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof, R ｂ is a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof, R ｃ is hydrogen, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof, the composition for a semiconductor photoresist according to claim 11.

13. The composition for a semiconductor photoresist according to Claim 1, wherein the organometallic compound containing Sn is represented by the following Chemical Formula 3 or Chemical Formula 4: 【Chemical Formula 7】 In the Chemical Formula 3, R ６ is a C1-C31 hydrocarbyl group, where 0 < z ≤ 2 and 0 < (z + x) ≤ 4; 【Chemical 8】 In the Chemical Formula 4, R ７ is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C4-C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof, X is sulfur (S), selenium (Se), or tellurium (Te), Y is -OR ｍ or -OC(=O)R ｎ and Said R ｍ is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof, R ｎ is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof, and n, m, l, and k are independently integers from 1 to 20.

14. Forming an etching target film on a substrate; Applying the composition for semiconductor photoresist according to any one of claims 1 to 13 on the etching target film to form a photoresist film; Patterning the photoresist film to form a photoresist pattern; and An etching step of using the photoresist pattern as an etching mask to etch the etching target film, which is a pattern formation method.

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