Semiconductor photoresist composition and method of forming patterns using the same

Abstract

To provide a semiconductor photoresist composition that can achieve excellent sensitivity and excellent coating properties.SOLUTION: The present invention relates to a semiconductor photoresist composition including: a Sn-containing organometallic compound; a carboxylic acid 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 5

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 elemental 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 (for example, 20 nm or less) can be formed in the exposure process of the semiconductor device manufacturing process.

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

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

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

[0006] To overcome the shortcomings of the chemically amplified organic photosensitive compositions described above, inorganic photosensitive compositions have been studied. In the case of inorganic photosensitive compositions, they are mainly used for negative tone patterning that has resistance to removal by a developer composition through chemical modification by a non-chemically amplified mechanism. In the case of inorganic compositions, they contain inorganic elements that have a higher EUV absorption rate compared to hydrocarbons, and it is known that sensitivity can be ensured even with a non-chemically amplified mechanism, and they are less sensitive to the stochastic effect, and also have fewer line edge roughness and 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 are deep ultraviolet (deep UV), x-ray, and electron beam sources and have been effective in patterning large features in a bilayer configuration. More recently, cationic hafnium metal oxide sulfate (HfSOx) materials with a peroxo complexing agent have shown impressive performance when used to image a 15 nm half-pitch (HP) by projection EUV lithography (US2011-0045406,; J.K. Stowers, A. Telecky, M. Kocsis, B.L. Clark, D.A. Keszler, A. Grenville, C.N. Anderson, P.P. Naulleau, Proc. SPIE, 7969, 796915, 2011). This system shows state-of-the-art performance for non-CA photoresists and has a photospeed approaching the requirements for a viable EUV photoresist. However, hafnium metal oxide sulfate materials with a peroxo complexing agent have some practical drawbacks. First, these materials are coated with a highly corrosive sulfuric acid / hydrogen peroxide mixture and do not have good shelf-life stability. Second, it is not easy to make structural changes for performance improvement as a composite mixture. Third, they must be developed with a very high concentration of about 25 wt% tetramethylammonium hydroxide (TMAH) solution or the like.

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

Summary of the Invention

Problems to be Solved by the Invention

[0010] One embodiment provides a composition for a semiconductor photoresist that is excellent in coating properties and sensitivity.

[0011] Another embodiment 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 contains a Sn-containing organometallic compound, a carboxylic acid compound represented by the following Chemical Formula 1, and a solvent.

Chemical Formula

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

Advantages of the Invention

[0014] A composition for a semiconductor photoresist according to an embodiment enables excellent sensitivity and excellent coating properties to be achieved.

Brief Description of the Drawings

[0015]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Mode for Carrying Out the Invention

[0016] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, in describing this specification, descriptions of already known functions or configurations are omitted for the sake of clarity of the gist of this specification.

[0017] For the sake of clarity of explanation, parts that are unnecessary for 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 the convenience of explanation, so this description is not necessarily limited to the illustration.

[0018] In the drawings, the thicknesses are shown enlarged to clearly represent various layers and regions. And in the drawings, for the convenience of explanation, the thicknesses of some layers and regions are exaggeratedly shown. When a part such as a layer, a film, a region, or a plate is said to be “above” another part, this includes not only the case where it is “directly above” the other part but also the case where there are further other parts in between.

[0019] In this description, "substituted" 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 as 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" that does not contain any double or triple bonds.

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

[0022] In this description, the 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, a C3-C6 cycloalkyl group, a C3-C5 cycloalkyl group, or a C3-C4 cycloalkyl group. For example, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and is not limited thereto.

[0024] 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 allyl group, a 1-propenyl group, a 1-methyl-1-propenyl group, a 2-propenyl group, a 2-methyl-2-propenyl group, a 1-propynyl group, a 1-methyl-1-propynyl group, a 2-propynyl group, a 2-methyl-2-propynyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group.

[0026] As used herein, the "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 a monocyclic or fused-ring polycyclic (i.e., a ring that shares adjacent pairs of carbon atoms) functional group.

[0027] As used herein, the term "heteroaryl group" means a group containing at least one heteroatom selected from the group consisting of N, O, S, P, and Si within an aryl group. Two or more heteroaryl groups may be directly linked by a sigma bond, or when the heteroaryl group contains two or more rings, the two or more rings may be fused to each other. When the heteroaryl group is a fused ring, each ring may contain 1 to 4 of the heteroatoms.

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

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

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

[0031] A composition for a semiconductor photoresist according to an embodiment of the present invention may include a Sn-containing organometallic compound, a carboxylic acid compound represented by the following Chemical Formula 1, and a solvent. [Chemical Formula] In Chemical Formula 1, R 5 ~R 7 are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7 or C30 arylalkyl group, a substituted or unsubstituted C1-C20 alkoxy group, -La -X 1 -R a (wherein X 1 is O or S, L a is a single bond or a substituted or unsubstituted C1-C20 alkylene group, and R a is hydrogen or a substituted or unsubstituted C1-C20 alkyl group), or -L b -N(R b )(R c (wherein L b is a single bond or a substituted or unsubstituted C1-C20 alkylene group, and R b and R c are each independently hydrogen or a substituted or unsubstituted C1-C20 alkyl group)) and, R 5 ~R 7 at least one of which is -L b -N(R b )(R c ).

[0032] The carboxylic acid compound represented by the chemical formula 1 is contained in an amount of 0.001 to 10% by weight based on 100% by weight of the composition for semiconductor photoresist.

[0033] For example, the carboxylic acid compound represented by the chemical formula 1 is contained in an amount of 0.005 to 10% by weight or 0.01 to 5% by weight based on 100% by weight of the composition for semiconductor photoresist.

[0034] 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.

[0035] By including the Sn-containing organometallic compound and the carboxylic acid compound in the above content ranges in the composition for semiconductor photoresist according to one embodiment, the sensitivity of the photoresist can be improved.

[0036] The composition for a semiconductor photoresist according to one embodiment can contain the Sn-containing organometallic compound and the carboxylic acid compound in a weight ratio of 99:1 to 90:10. For example, the semiconductor photoresist composition can contain the Sn-containing organometallic compound and the carboxylic acid compound represented by Chemical Formula 1 in a weight ratio of 95:5 to 90:10.

[0037] When the weight ratio of the Sn-containing organometallic compound and the carboxylic acid compound satisfies the above range, a composition for a semiconductor photoresist having excellent sensitivity can be provided.

[0038] The Sn-containing organometallic compound can contain at least one of an organic oxy group and an organic carbonyloxy group.

[0039] The Sn-containing organometallic compound is represented by the following Chemical Formula 2.

Chemical Formula

[0040] In one embodiment, the R 9 ~R 11 at least one of is alkoxo and aryloxo (-OR d , where R d is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), and carboxyl group (-O(C=O)R e , R e is selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof).

[0041] On the other hand, the compound represented by Chemical Formula 2 can exhibit excellent limit resolution for the pattern formed using the semiconductor photoresist composition containing it by containing -OR d or -OC(=O)R e .

[0042] Also, the ligand of -OR d or -OC(=O)R e can determine the solubility of the compound represented by Chemical Formula 2 in the solvent.

[0043] The R 8is 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 d 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 e 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.

[0044] Said R 8 is a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propenyl group, a butenyl group, an ethynyl group, a propynyl group, a butynyl group, a phenyl group, a tolyl group, a xylyl group, a benzyl group, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pentanoyl group, an ethoxy group, a propoxy group, or a combination thereof, R d is an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propenyl group, a butenyl group, an ethynyl group, a propynyl group, a butynyl group, a phenyl group, a tolyl group, a xylyl group, a benzyl group, or a combination thereof, R eIt may be hydrogen, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propenyl group, a butenyl group, an ethynyl group, a propynyl group, a butynyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, or a combination thereof.

[0045] Further, the Sn-containing organometallic compound is represented by the following Chemical Formula 3 or Chemical Formula 4.

Chemical Formula

Chemical Formula

[0046] The solvent contained in the semiconductor photoresist composition according to one embodiment may be an organic solvent, and examples thereof 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 are not limited thereto.

[0047] The semiconductor resist composition according to one embodiment may further contain a resin in addition to the Sn-containing organometallic compound, carboxylic acid compound, and solvent.

[0048] The resin may be a phenolic resin containing at least one aromatic moiety listed in Group 2 below.

[0049]

Chemical formula

[0050] The resin is contained in an amount of 0.1 wt% to 50 wt% based on the total content of the semiconductor photoresist composition.

[0051] When the resin is contained within the above content range, excellent etching resistance and heat resistance can be achieved.

[0052] On the other hand, the semiconductor photoresist composition preferably consists of the above-described Sn-containing organometallic compound, carboxylic acid compound, solvent, and resin.

[0053] The semiconductor photoresist composition according to the above-described embodiment may further contain an additive in some cases. Examples of the additive include a surfactant, crosslinking agent, leveling agent, organic acid, quencher, or a combination thereof.

[0054] As the surfactant, for example, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, or a combination thereof can be used, but it is not limited thereto.

[0055] Examples of the crosslinking agent include, but are not limited to, melamine-based crosslinking agents, substituted iodine-based crosslinking agents, acrylic-based crosslinking agents, epoxy-based crosslinking agents, or polymer-based crosslinking agents. As a crosslinking agent having at least two crosslinking-forming substituents, for example, compounds such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, acrylmethacrylate, 1,4-butanediol diglycidyl ether, glycidol, diglycidyl 1,2-cyclohexanedicarboxylate, trimethylolpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated iodine, butoxymethylated iodine, or methoxymethylated thioiodine can be used.

[0056] The leveling agent is for improving the coating flatness during printing, and known leveling agents available by commercial methods can be used.

[0057] The organic acid may be, but is not limited to, p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, fluorinated sulfonium salt, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or a combination thereof.

[0058] The inhibitor may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0059] In one embodiment, an acid compound different from the above-described carboxylic acid compound can be mixed with the composition for a semiconductor photoresist according to the present invention, and examples of the mixable acid compound include organic acids, sulfonic acids, phosphonic acids, and the like.

[0060] The usage amounts of these additives can be easily adjusted according to the desired physical properties and may be omitted.

[0061] In addition, the composition for semiconductor photoresist can further use a silane coupling agent as an adhesion promoter (for example, to improve the adhesion between the composition for semiconductor photoresist and a substrate) in order to improve the adhesion to the substrate and the like. The silane coupling agent can be, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; carbon-carbon unsaturated bond-containing silane compounds such as trimethoxy[3-(phenylamino)propyl]silane, etc., but is not limited thereto.

[0062] The composition for semiconductor photoresist does not cause pattern collapse even when forming a pattern having a high aspect ratio. Therefore, for example, for forming a fine pattern having a width of 5 nm to 100 nm, for example, a fine pattern having a width of 5 nm to 80 nm, for example, a fine pattern having a width of 5 nm to 70 nm, for example, a fine pattern having a width of 5 nm to 50 nm, for example, a fine pattern having a width of 5 nm to 40 nm, for example, a fine pattern having a width of 5 nm to 30 nm, for example, a fine pattern having a width of 5 nm to 20 nm, it can be used in a photoresist process using light with a wavelength of 5 nm to 150 nm, for example, a photoresist process using light with a wavelength of 5 nm to 100 nm, for example, a photoresist process using light with a wavelength of 5 nm to 80 nm, for example, a photoresist process using light with a wavelength of 5 nm to 50 nm, for example, a photoresist process using light with a wavelength of 5 nm to 30 nm, for example, a photoresist process using light with a wavelength of 5 nm to 20 nm. Therefore, when using the composition for semiconductor photoresist according to one embodiment, extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5 nm can be realized.

[0063] On the other hand, according to another embodiment, a method of forming a pattern using the above-described composition for a semiconductor photoresist can be provided. As an example, the manufactured pattern may be a photoresist pattern.

[0064] The pattern formation method according to one embodiment includes a step of forming a film to be etched on a substrate, a step of applying the above-described composition for a semiconductor photoresist on the film to be etched to form a photoresist film, a step of patterning the photoresist film to form a photoresist pattern, and a step of etching the film to be etched using the photoresist pattern as an etching mask.

[0065] Hereinafter, a method of forming a pattern using the above-described composition for a semiconductor photoresist will be described with reference to FIGS. 1 to 5. FIGS. 1 to 5 are cross-sectional views for explaining a pattern formation method using the composition for a semiconductor photoresist according to the present invention.

[0066] Referring to FIG. 1, first, an object to be etched is provided. As an example of the object to be etched, it may be a thin film 102 formed on a semiconductor substrate 100. Hereinafter, the description will be made only in the case where the object to be etched is the thin film 102. In order to remove contaminants remaining on the surface of the thin film 102, the surface of the thin film 102 is cleaned. The thin film 102 may be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film.

[0067] Next, a composition for forming a resist underlayer film for forming a resist underlayer film 104 is coated on the surface of the cleaned thin film 102 by applying a spin coating method. However, one embodiment is not necessarily limited thereto, and various known coating methods, for example, spray coating, dip coating, knife edge coating, printing methods such as inkjet printing and screen printing, etc. may be used.

[0068] The coating process of the resist underlayer film can be omitted, and hereinafter, the case of coating the resist underlayer film will be described.

[0069] 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.

[0070] The resist underlayer film 104 is formed between the substrate 100 and the photoresist film 106, and when the irradiation rays reflected from the interface between the substrate 100 and the photoresist film 106 or the interlayer hardmask scatter into the unintended photoresist region, it can prevent the non-uniformity of the photoresist linewidth and the pattern formation property.

[0071] Referring to FIG. 2, the above-described semiconductor photoresist composition is coated on the resist underlayer film 104 to form a photoresist film 106. The photoresist film 106 may be in a form cured by a heat treatment process after coating the above-described semiconductor photoresist composition on the thin film 102 formed on the substrate 100.

[0072] More specifically, the step of forming a pattern using the semiconductor photoresist composition includes a step of applying the above-described semiconductor photoresist composition on the substrate 100 on which the thin film 102 is formed by spin coating, slit coating, inkjet printing, etc., and a step of drying the applied semiconductor photoresist composition to form a photoresist film 106.

[0073] Since the semiconductor photoresist composition has already been described in detail, duplicate description will be omitted.

[0074] Next, 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.

[0075] Referring to FIG. 3, the photoresist film 106 is selectively exposed using the patterned mask 110.

[0076] As an example, examples of the light that can be used in the exposure process include not only light having a short wavelength such as activation irradiation line i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), but also light having a high energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm), E-Beam (electron beam), and the like.

[0077] More specifically, the exposure light according to one embodiment may be short-wavelength light having a wavelength range of 5 nm to 150 nm, or may be light having a high energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm), E-Beam (electron beam), and the like.

[0078] The exposed region 106a in the photoresist film 106 has a different solubility from the unexposed region 106b of the photoresist film 106 by forming a polymer through a crosslinking reaction such as condensation between organometallic compounds.

[0079] Next, a second baking process is performed on the substrate 100. The second baking process can be performed at a temperature of about 90°C to about 200°C. By performing the second baking process, the exposed region 106a of the photoresist film 106 becomes less soluble in the developer.

[0080] FIG. 4 shows a photoresist pattern 108 formed by dissolving and removing the photoresist film 106b corresponding to the unexposed region using a developer. Specifically, after dissolving the photoresist film 106b corresponding to the unexposed region using an organic solvent such as 2 - heptanone and then removing it, the photoresist pattern 108 corresponding to the negative - tone image is completed.

[0081] As described above, the developer used in the pattern - forming method according to an embodiment may be an organic solvent. Examples of the organic solvent used in the pattern - forming method according to an embodiment include 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.

[0082] However, the photoresist pattern according to an embodiment is not necessarily limited to the formation of a negative - tone image and may be formed to have a positive - tone image. In this case, examples of the developer that can be used for positive - tone image formation include quaternary ammonium hydroxide compositions such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof.

[0083] As described above, the photoresist pattern 108 formed by exposure with light having wavelengths such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), etc., 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. As an example, the photoresist pattern 108 is formed with a width of 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.

[0084] On the other 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 having 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.

[0085] Next, the resist underlayer film 104 is etched using the photoresist pattern 108 as an etching mask. In such an etching process, an organic film pattern 112 is formed. The formed organic film pattern 112 can also have a width corresponding to the photoresist pattern 108.

[0086] Referring to FIG. 5, the thin film 102 exposed by applying the photoresist pattern 108 as an etching mask is etched. As a result, the thin film is formed into a thin film pattern 114.

[0087] 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.

[0088] In the previously performed exposure process, the thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process performed using an EUV light source can have a width corresponding to that of the photoresist pattern 108. As an example, it can have the same width as the photoresist pattern 108, which can be 5 nm to 100 nm. For example, the thin film pattern 114 formed by the exposure process performed using an EUV light source can have widths such as 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, 5 nm to 20 nm, similar to the photoresist pattern 108, and more specifically, it may be formed with a width of 20 nm or less.

Example

[0089] Hereinafter, the present invention will be described in more detail through examples related to the production of the above-described composition for semiconductor photoresist. However, the technical features of the present invention are not limited by the following examples.

[0090] 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.

[0091] Remove unreacted propionic acid under reduced pressure to obtain a compound represented by the following Chemical Formula 5.

Chem.

[0092] 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. After the reaction is completed, filter, concentrate, and vacuum dry to obtain a compound represented by the following Chemical Formula 6.

Chem.

[0093] Synthesis Example 3 After dissolving 10 g of dibutyltin dichloride in 30 mL of ether, 70 mL of a 1 M aqueous sodium hydroxide (NaOH) solution was added, followed by stirring for 1 hour. After stirring, the resulting solid was filtered, washed three times with 25 mL of deionized water, and then dried 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]

[0094] Production of Composition for Semiconductor Photoresist Examples 1 to 3 and Comparative Examples 1 to 5 The compounds represented by Chemical Formulas 5 to 7 obtained in Synthesis Examples 1 to 3 and the carboxylic acid compound were dissolved in propylene glycol methyl ether acetate (PGMEA) at a concentration of 3 wt% at the weight ratios shown in Table 1 below, and filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to produce compositions for semiconductor photoresist according to Examples 1 to 3 and Comparative Examples 1 to 5.

[0095] [Table 1]

[0096] Evaluation 1: Sensitivity and Line Edge Roughness (LER) Evaluation On a 200 mm circular silicon wafer whose surface was vapor-deposited with HMDS, the photoresist compositions according to the above Examples and Comparative Examples were spin-coated at 1500 rpm for 30 seconds each, baked at 110 °C for 60 seconds (post-apply bake, PAB), and then left at room temperature (23 ± 2 °C) for 30 seconds.

[0097] After that, 50 circular pads in a linear array with a diameter of 500 μm were projected onto the wafer coated with the composition for photoresist using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). The pad exposure time was adjusted so that the EUV increased dose was applied to each pad.

[0098] Thereafter, the resist and the substrate were exposed on a hot plate at 160 °C for 120 seconds and then baked. The baked film was developed with a PGMEA solvent to form a negative tone image. Finally, hot plate baking was performed at 150 °C for 2 minutes to terminate the process.

[0099] The thickness of the residual resist of the exposed pads was measured using ellipsometry. The remaining thickness was measured for each exposure amount and graphed as a function of the exposure amount to measure the sensitivity. After measuring the LER from the FE-SEM image, the sensitivity and line edge roughness were evaluated according to the following criteria, and the results are shown in Table 2.

[0100] [Evaluation criteria for sensitivity] -A: Less than 16 mJ / cm 2 Less than -B: 16 mJ / cm or more 2 or more

[0101] [Evaluation criteria for LER] -○: 2 nm or less -△: More than 2 nm and 5 nm or less -X: More than 5 nm

[0102] Evaluation 2: Surface roughness evaluation The photoresist compositions according to Examples 1 to 3 and Comparative Examples 1 to 5 were spin-coated on a wafer at 1500 rpm for 60 seconds, baked at 110°C for 60 seconds to form a thin film, and then the surface roughness of the thin film was measured using software (e.g., optical profiler) from an image taken by an atomic force microscope (AFM) according to the following criteria, and the results are shown in Table 2.

[0103] Among the surface roughness, the root mean square roughness (R q ;rms) means the root mean square (rms) of the vertical values within the reference length of the roughness profile.

[0104] [Evaluation Criteria for Surface Roughness] - ○: Rq less than 0.4 - X: Rq 0.4 or more

[0105]

Table 2

[0106] From the results in Table 2, it can be confirmed that the patterns formed using the semiconductor photoresist compositions according to Examples 1 to 3 have improved excellent sensitivity, LER, and coating properties compared to Comparative Examples 1 to 5.

[0107] As described above, specific embodiments of the present invention have been described and illustrated, but the present invention is not limited to the described embodiments, and it is obvious to those having ordinary knowledge in this technical field that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modified examples or variations should not be individually understood from the technical idea or perspective of the present invention, and the modified embodiments belong to the scope of the claims of the present invention.

Explanation of Reference Signs

[0108] 100… Substrate, 102… Thin film, 104… Lower resist film, 106… Photoresist film, 106a… Exposed area, 106b… Unexposed area, 108… Photoresist pattern, 112… Organic film pattern, 110… Patterned mask, 114… Thin film pattern.

Claims

1. An organometallic compound containing Sn; A carboxylic acid compound represented by the following Chemical Formula 1; and A solvent A composition for a semiconductor photoresist, comprising the above. 【Chemical 1】 In the above Chemical Formula 1, R ５ to R ７ each independently represents hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7 or C30 arylalkyl group, a substituted or unsubstituted C1-C20 alkoxy group, -L ａ -X １ -R ａ (where X １ is O or S, and L ａ is a single bond or a substituted or unsubstituted C1-C20 alkylene group, and R ａ is hydrogen or a substituted or unsubstituted C1-C20 alkyl group), or -L ｂ -N(R ｂ )(R ｃ )(where L ｂ is a single bond or a substituted or unsubstituted C1-C20 alkylene group, and R ｂ and R ｃ each independently represents hydrogen or a substituted or unsubstituted C1-C20 alkyl group) and R ５ ~R ７ At least one of them is -L ｂ -N(R ｂ )(R ｃ ) is.

2. The composition for a semiconductor photoresist according to Claim 1, wherein the carboxylic acid compound is contained in an amount of 0.001 to 10% by weight based on 100% by weight of the composition for a semiconductor photoresist.

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

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

5. The composition for a semiconductor photoresist according to Claim 1, wherein the Sn-containing organometallic compound and the carboxylic acid compound are contained in a weight ratio of 99:1 to 90:

10.

6. 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.

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

8. The composition for a semiconductor photoresist according to Claim 1, wherein the Sn-containing organometallic compound is represented by the following Chemical Formula 2: 【Chemical Formula 2】 In the above Chemical Formula 2, R ８ is selected from a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C6-C30 arylalkyl group, R ９ to R １１ 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, alkoxo and aryloxo (-OR ｄ , where R ｄ 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 ｅ , R ｅ is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an alkylamide or dialkylamide (-NR ｆ R ｇ , where R ｆ and R ｇ are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an amidato (-NR ｈ (COR ｉ ), where R ｈ and R ｉ is, independently of one another, hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidinato (-NR ｊ C(NR ｋ )R ｌ , where R ｊ , R ｋ and R ｌ are, independently of one another, hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (-SR ｍ , where 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) or a thiocarboxyl group (-S(CO)R ｎ , 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 R ９ ~R １１ At least one of which is alkoxo and aryloxo (-OR ｄ , where R ｄ 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(C=O)R ｅ , R ｅ is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an alkylamide or dialkylamide (-NR ｆ R ｇ , where R ｆ and R ｇ are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an amidato (-NR ｈ (C=OR ｉ ), where R ｈ and R ｉ are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an amidinato (-NR ｊ C(NR ｋ )R ｌ , where R ｊ , R ｋ and R ｌ is, independently of each other, hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (-SR ｍ , where 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) and a thiocarboxyl group (-S(C=O)R ｎ , R ｎ is selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof).

9. Said R ９ to R １１ at least one of which is alkoxo and aryloxo (—OR ｄ , where R ｄ is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), and a carboxyl group (—O(C═O)R ｅ , R ｅ is selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), the composition for a semiconductor photoresist according to claim 8.

10. Said R ８ 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 ｄ 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 ｅ is a hydrogen, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof, the composition for a semiconductor photoresist according to claim 8.

11. The composition for a semiconductor photoresist according to Claim 1, wherein the Sn-containing organometallic compound is represented by the following Chemical Formula 3 or Chemical Formula 4: [Chemical 3] In the above Chemical Formula 3, R １２ is a C1-C31 hydrocarbyl group, where 0 < z ≤ 2 and 0 < (z + x) ≤ 4; 【Chemical 4】 In the above Chemical Formula 4, R １３ 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, n2, m1, l1, and k1 are each independently an integer from 1 to 20.

12. Forming an etching target film on a substrate; Applying the composition for a semiconductor photoresist according to any one of Claims 1 to 11 on the etching target film to form a photoresist film; Patterning the photoresist film to form a photoresist pattern; and An etching target film is etched using the photoresist pattern as an etching mask, including a pattern forming method.

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