Photoresist composition and method of fabricating semiconductor device

Abstract

A photoresist composition is provided comprising: a photosensitive polymer having a protecting group; a photoacid generator (PAG); a metal precursor capable of generating metal ions and secondary electrons upon irradiation with light of 13.5 nm; and a solvent. Using the photoresist composition of the present invention has the effect of providing excellent resolution, improved productivity, and improved etch resistance.

Description

Technology Field

[0001] The present invention relates to a photoresist composition and a method for manufacturing a semiconductor device, and more specifically, to a photoresist composition and a method for manufacturing a semiconductor device that can have excellent resolution, improved productivity, and improved etch resistance. Background Technology

[0002] Due to advancements in electronic technology, the down-scaling of semiconductor devices has been progressing rapidly in recent years. Consequently, photolithography processes that are advantageous for realizing fine patterns are required. In particular, in photolithography processes for manufacturing integrated circuit devices, there is a need to develop technology that can increase light sensitivity and improve the dissolution contrast with respect to the developer between the exposed and unexposed areas of the photoresist film. The problem to be solved

[0003] The first technical objective of the present invention is to provide a photoresist composition that can have excellent resolution, improved productivity, and enhanced etch resistance.

[0004] The second technical objective of the present invention is to provide a method for manufacturing a semiconductor device that can have excellent resolution, improved productivity, and improved etch resistance. means of solving the problem

[0005] To achieve the first technical objective, the present invention provides a photoresist composition comprising: a photosensitive polymer having a protecting group; a photoacid generator (PAG); a metal precursor capable of generating metal ions and secondary electrons upon irradiation with light of 13.5 nm; and a solvent.

[0006] Another aspect of the present invention provides a photoresist composition comprising: a photosensitive polymer having a protecting group and a polydispersity index (PI) of 2 to 3; a photoacid generator (PAG); a metal precursor having a structure in which an organic ligand is coordinately bonded to a metal atom and capable of generating metal ions and secondary electrons upon irradiation with light of 13.5 nm; and a solvent, wherein the metal precursor has a structure of the following chemical formula (I), and the photoacid generator is included in an amount of 25% to 50% by weight based on the total weight of the photosensitive polymer.

[0007] M n L m (I)

[0008] (wherein M is one or more selected from the group consisting of polonium (Po), tellurium (Te), titanium (Ti), lead (Pb), gold (Au), silver (Ag), cesium (Cs), bismuth (Bi), tin (Sn), zinc (Zn), antimony (Sb), indium (In), cadmium (Cd), and astatine (At), and L is a halogen, a straight-chain or branched alkyl group having 2 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an allyl group having 3 to 15 carbon atoms, a carboxylate group having 2 to 20 carbon atoms, or a cycloalkyl group having 2 to 20 carbon atoms (It is a (meth)acrylate group, where n is an integer from 1 to 12, and m is an integer from 2 to 72, which is an integer from 2n to 6n)

[0009] Another aspect of the present invention provides a photoresist composition comprising: a photosensitive polymer having a protecting group and a polydispersity index (PI) of 2 to 3; a photoacid generator (PAG) capable of generating acid upon irradiation with light of 13.5 nm; a metal precursor having a structure in which an organic ligand is coordinately bonded to a metal atom and having the structure of the following chemical formula (I); and a solvent, wherein the photoacid generator is included in an amount of 25% to 50% by weight based on the total weight of the photosensitive polymer.

[0010] M n L m (I)

[0011] (Here, M is the atomic absorption cross-section for light irradiation of 13.5 nm, 5x10 6 cm 2 / mol or more of a metal element, where L is a halogen, a straight-chain or branched alkyl group having 2 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an alkoxy group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an allyl group having 3 to 15 carbon atoms, a carboxylate group having 2 to 20 carbon atoms, or a (meth)acrylate group having 2 to 20 carbon atoms, where n is an integer from 1 to 12, and m is an integer from 2 to 72, which is an integer from 2n to 6n)

[0012] Another aspect of the present invention comprises a photosensitive polymer having a polydispersity index (PI) of 2 to 3; a photogenerator; and a metal precursor having a structure in which an organic ligand is coordinately bonded to a metal atom, wherein the metal precursor is tin(II) ethoxide, tin(IV) n-butoxide, tin(IV) tert- A photoresist composition comprising one or more of butoxide, tin(IV) acetate, tin(II) 2-ethylhexanoate, dibutyl tin chloride, lead(II) acetate hydrate, zinc acetate hydrate, and titanium(IV) isopropoxide, in an amount of 5% to 10% by weight based on the total weight of the photosensitive polymer; a basic quencher; and a solvent; wherein the photogenerator is included in an amount of 25% to 50% by weight based on the total weight of the photosensitive polymer.

[0013] To achieve the second technical objective, the present invention provides a method for manufacturing a semiconductor device comprising: a step of forming a photoresist material layer using a photoresist composition on a substrate; a first baking step of performing a first baking on the photoresist material layer; an exposure step of irradiating a portion of the photoresist material layer where the first baking was performed with a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F2 excimer laser (157 nm), or EUV light (13.5 nm); a second baking step of performing a second baking on the photoresist material layer after the exposure step; a step of removing an unexposed portion of the photoresist material layer where the second baking was performed in order to form a photoresist pattern; and a step of processing the substrate using the photoresist pattern. In this case, the photoresist composition comprises a photosensitive polymer having a protecting group; a photoacid generator (PAG); It includes a metal precursor capable of generating metal ions and secondary electrons by light irradiation in the above exposure step; and a solvent. Effects of the invention

[0014] Using the photoresist composition of the present invention has the effect of providing excellent resolution, improved productivity, and enhanced etch resistance. Brief explanation of the drawing

[0015] FIG. 1 is a schematic diagram conceptually illustrating a mechanism in which a photoresist composition according to one embodiment of the present invention is cured by exposure and post-exposure bake (PEB). FIG. 2 is a flowchart illustrating a method for manufacturing an integrated circuit element according to embodiments of the technical concept of the present invention. FIGS. 3a to 3e are cross-sectional views illustrated in the order of process to explain a method for manufacturing an integrated circuit element according to embodiments of the technical concept of the present invention. FIGS. 4a and FIGS. 4b are schematic diagrams illustrating EUV exposure performed on a photoresist film on a feature layer. Figure 5 is a schematic diagram illustrating an exemplary process in which a photosensitive polymer is crosslinked by a metal precursor. Figure 6 is a graph showing the ratio of the remaining film after patterning with the photoresist compositions of Example 1 and Comparative Example 1 according to exposure dose. Specific details for implementing the invention

[0016] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. Identical components in the drawings are denoted by the same reference numerals, and redundant descriptions thereof are omitted.

[0017] A photoresist composition according to one embodiment of the present invention comprises a photosensitive polymer, a photoacid generator (PAG), a metal precursor, and a solvent.

[0018] photosensitive polymer

[0019] The above photosensitive polymer may be a polymer capable of causing a photochemical reaction by irradiation with a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F2 excimer laser (157 nm), or EUV light (13.5 nm), particularly by irradiation with EUV light.

[0020] In some embodiments, the solubility of the photosensitive polymer in the developer may be increased by the photochemical reaction. In some embodiments, the photosensitive polymer may have a protecting group attached to a repeating unit, and the protecting group may be an acid-labile functional group and may be deprotected by an acid generated during the exposure step, thereby allowing the photosensitive polymer to dissolve well in the developer. Additionally, the deprotected protecting group may perform a chemical amplification action by generating a new acid.

[0021] (Polyhydroxystyrene resin)

[0022] In some embodiments, the photosensitive polymer may be a polyhydroxystyrene (PHS) resin. For example, the PHS resin may be a resin having repeating units represented by the following chemical formula 1.

[0023] [Chemical Formula 1]

[0024]

[0025] Here, R 1a is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 1bIt is a protective organ of acid dissociation. Specific examples of the above protecting group include a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a vinyloxyethyl group, a tetrahydropyranyl group, a tetrafuranyl group, a trialkylsilyl group, an isonorbornyl group, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, 3-tetrahydrofuranyl, 3-oxocyclohexyl, γ-butyllactone-3-yl, mavaloniclactone, γ-butyrolactone-2-yl, 3-methyl-γ-butyrolactone-3-yl, 2-tetrahydropyranyl, and 2-tetrahydrofuranyl. (2-tetrahydrofuranyl), 2,3-propylenecarbonate-1-yl, 1-methoxyethyl, 1-ethoxyethyl, 1-(2-methoxyethoxy)ethyl, 1-(2-acetoxyethoxy)ethyl), t-butoxycarbonylmethyl, methoxymethyl, ethoxymethyl, trimethoxysilyl, triethoxysilyl, methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, isobutoxyethyl group, tert-butoxyethyl group, It may be a cyclohexyloxyethyl group, a methoxypropyl group, an ethoxypropyl group, a 1-methoxy-1-methyl-ethyl group, a 1-ethoxy-1-methylethyl group, a tert-butoxycarbonyl group (tert-butoxycarbonyl, t-BOC), or a tert-butoxycarbonylmethyl group.Examples of the above straight-chain or branched alkyl groups include methyl groups, ethyl groups, propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, tert-butyl groups, pentyl groups, isopentyl groups, neopentyl groups, etc. In addition, examples of the above cyclic alkyl groups include cyclopentyl groups, cyclohexyl groups, etc.

[0026] In some embodiments, the PHS resin may further include other polymerizable compounds as repeating units. Such polymerizable compounds include, for example, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having carboxyl groups and ester bonds such as 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid, and 2-methacryloyloxyethylhexahydrophthalic acid; and (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate. (Meth)acrylate hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; (meth)acrylate aryl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; Examples include polymerizable compounds containing amide bonds, such as acrylamide and methacrylamide. However, the present invention is not limited thereto.

[0027] (Acrylic resin)

[0028] In some embodiments, the photosensitive polymer may be an acrylic resin. For example, the acrylic resin may be a resin having repeating units represented by the following chemical formula 2.

[0029] [Chemical Formula 2]

[0030]

[0031] Here, R 2a is a hydrogen atom, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a straight-chain or branched fluorinated alkyl group having 1 to 6 carbon atoms, and R 2b is an acid-dissociating protecting group, and its specific type is as described in relation to Chemical Formula 1.

[0032] In some embodiments, the photosensitive polymer may be composed of a (meth)acrylate-based polymer. The (meth)acrylate-based polymer may be an aliphatic (meth)acrylate-based polymer and may be composed, for example, of polymethylmethacrylate (PMMA), poly(t-butylmethacrylate), poly(methacrylic acid), poly(norbornylmethacrylate), a binary or terpolymer of repeating units of the (meth)acrylate-based polymers, or a combination thereof.

[0033] In some embodiments, the acrylic resin may further include other polymerizable compounds as repeating units. Such polymerizable compounds include, for example, ether-linked acrylates such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate; monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid; and dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid. Methacrylic acid derivatives having carboxyl groups and ester bonds, such as 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid, and 2-methacryloyloxyethylhexahydrophthalic acid; alkyl (meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and cyclohexyl (meth)acrylate; hydroxyalkyl (meth)acrylates, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; aryl (meth)acrylates, such as phenyl (meth)acrylate and benzyl (meth)acrylate; and dicarboxylic acid diesters, such as diethyl maleate and dibutyl fumarate. Examples include vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and amide bond-containing polymerizable compounds such as acrylamide and methacrylamide. However, the present invention is not limited thereto.

[0034] In some embodiments, the photosensitive polymer may be a copolymer comprising a first repeating unit identical to the repeating unit of Formula 2 and a second repeating unit identical to the repeating unit of Formula 1. The first repeating unit and the second repeating unit may be copolymerized in a random or block form. In some embodiments, the first repeating unit and the second repeating unit may be copolymerized randomly.

[0035] In some embodiments, a protector is provided in the first repetition unit and R of the second repetition unit 1b may be a hydroxyl group or a carboxyl group. In some embodiments, the second repeating unit may include one or more of the moiety listed in Formula 3 below.

[0036] [Chemical Formula 3]

[0037]

[0038] (Here, "*" indicates the joining position)

[0039] In some embodiments, a protector is provided in the second repetition unit and R of the first repetition unit 2b It can be a hydrogen atom.

[0040] The photosensitive polymer may have a weight average molecular weight (Mw) of about 10,000 to about 600,000. In some embodiments, the photosensitive polymer may have an Mw of about 20,000 to about 400,000, or about 30,000 to about 300,000. In some embodiments, the Mw may be a value measured by gel permeation chromatography (GPC) with polystyrene as a standard.

[0041] The photosensitive polymer may have a polydispersity index (PI) of 1 to about 3. The content of the photosensitive polymer may be about 5 wt% to about 60 wt% with respect to the total weight of the photoresist composition.

[0042] photoacid generator (PAG)

[0043] In exemplary embodiments, the photoresist composition according to the embodiments of the technical concept of the present invention may further include a photoacid generator (PAG) that generates acid upon exposure.

[0044] The above PAG may be composed of a material having a chemical structural formula different from the chemical structural formula of the above photodegradable compound. For example, the above PAG may generate acid when exposed to light selected from a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F2 excimer laser (157 nm), and an EUV laser (13.5 nm). The above PAG may be composed of a material that generates a relatively strong acid having a pKa (acid dissociation constant) of about -20 or higher and about less than 1 upon exposure. The above PAG may be composed of, for example, triarylsulfonium salts, diaryliodonium salts, sulfonates, or a mixture thereof. For example, the above PAG is triphenylsulfonium triflate, triphenylsulfonium antimonate, triphenylsulfonium difluoroalkyl sulfonate, diphenyliodonium triflate, diphenyliodonium antimonate, methoxydiphenyliodonium triflate, di-t-butyldiphenyliodonium triflate, 2,6-dinitrobenzyl sulfonates, pyrogallol tris(alkylsulfonates), N-hydroxysuccinimide triflate, norbornene-dicarboximide-triflateTriphenylsulfonium nonaflate, diphenyliodonium nonaflate, methoxydiphenyliodonium nonaflate, di-t-butyldiphenyliodonium nonaflate, N-hydroxysuccinimide nonaflate, norbornene-dicarboximide-nonaflate, triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluorooctanesulfonate (PFOS), diphenyliodonium PFOS, methoxydiphenyliodonium PFOS It may consist of methoxydiphenyliodonium PFOS, di-t-butyldiphenyliodonium triflate, N-hydroxysuccinimide PFOS, norbornene-dicarboximide PFOS, or a mixture thereof.

[0045] In a photoresist composition according to embodiments of the technical concept of the present invention, the PAG may be included in an amount of about 0.1 wt% to about 5.0 wt% based on the total weight of the chemically amplified polymer. In some embodiments, the PAG may include about 1 wt% to about 48 wt%, about 3 wt% to about 46 wt%, about 5 wt% to about 44 wt%, about 7 wt% to about 42 wt%, about 10 wt% to about 40 wt%, about 15 wt% to about 38 wt%, or any amount between these values ​​based on the total weight of the chemically amplified polymer.

[0046] metal precursor

[0047] The above metal precursor may have a structure in which an organic ligand is coordinately bonded to a metal atom, and specifically, may have the structure of Chemical Formula 4 below.

[0048] [Chemical Formula 4]

[0049] M n L m

[0050] (Here, M is the atomic absorption cross-section for light irradiation of 13.5 nm, 5x10 6 cm 2 / mol or more of a metal element, where L is a halogen, a straight-chain or branched alkyl group having 2 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an alkoxy group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an allyl group having 3 to 15 carbon atoms, a carboxylate group having 2 to 20 carbon atoms, or a (meth)acrylate group having 2 to 20 carbon atoms, where n is an integer from 1 to 12, and m is an integer from 2 to 72, which is an integer from 2n to 6n)

[0051] The metal precursor is configured to emit secondary electrons by irradiation with a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F2 excimer laser (157 nm), or EUV light (13.5 nm), particularly by irradiation with EUV light, thereby generating metal ions.

[0052] In some embodiments, the metal element M has an atomic absorption cross section of 5x10 for light irradiation of 13.5 nm. 6 cm 2 It may be a metal element with a mole or more. Specifically, the metal element M may be one or more selected from the group consisting of polonium (Po), tellurium (Te), titanium (Ti), lead (Pb), gold (Au), silver (Ag), cesium (Cs), bismuth (Bi), tin (Sn), zinc (Zn), antimony (Sb), indium (In), cadmium (Cd), and astatine (At).

[0053] In some embodiments, L may have the structure -XR as an organic ligand (wherein R is an alkyl group having 1 to 11 carbon atoms, and -X- is -O- or -COO-). In some embodiments, L is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 1,2-dimethylbutoxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, n-octyloxy, n-nonyloxy, n-decyloxy, acetate, propionate, butyrate, pentanoate, valerate, hexanoate, heptylate, caprylate, pelargonate, decanoate, undecanoate, laurate, stearate, It can be selected from the group consisting of pivalate and benzoate.

[0054] In some embodiments, the metal precursor is tin(II) ethoxide, tin(IV) n-butoxide, tin(IV) tert - It may be one or more of butoxide, tin(IV) acetate, tin(II) 2-ethylhexanoate, dibutyl tin chloride, lead(II) acetate hydrate, zinc acetate hydrate, and titanium(IV) isopropoxide.

[0055] In a photoresist composition according to embodiments of the technical concept of the present invention, the metal precursor may be in an amount of about 2% to about 10% by weight, about 3% to about 7.5% by weight, or about 4% to about 6% by weight based on the total weight of the chemically amplified polymer. If the content of the metal precursor is too low, the effect of adding the metal precursor may be insufficient. If the content of the metal precursor is too high, the resolution of the pattern may be excessively reduced.

[0056] menstruum

[0057] The solvent included in the above photoresist composition may be an organic solvent. The organic solvent may include at least one of ether, alcohol, glycol ether, aromatic hydrocarbon compound, ketone, and ester, but is not limited thereto. For example, the organic solvent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol, propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether, propylene glycol butyl ether acetate, ethanol, propanol, isopropyl alcohol, isobutyl alcohol, 4-methyl-2-pentanol (methyl isobutyl carbion: MIBC), hexanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol, propylene glycol, heptanone, propylene carbonate, butylene carbonate, toluene, xylene, Methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-ethyl hydroxypropionate, 2-ethyl hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-methyl hydroxy-3-methylbutanoate, 3-methyl methoxypropionate, 3-ethyl methoxypropionate, 3-ethyl ethoxypropionate, 3-methyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, gamma-butyrolactone, methyl 2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, It may consist of 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate, or a combination thereof.

[0058] In a photoresist composition according to embodiments of the technical concept of the present invention, the solvent may be included in the remainder excluding the content of the main components including the metal structure, the radical quencher, and the photobase generator. In exemplary embodiments, the solvent may be included in an amount of about 0.1 weight% to about 99.7 weight% based on the total weight of the photoresist composition.

[0059] FIG. 1 is a schematic diagram conceptually illustrating a mechanism in which a photoresist composition according to one embodiment of the present invention is cured by exposure and post-exposure bake (PEB).

[0060] Referring to FIG. 1, the photoresist composition comprises a photosensitive polymer, PAG, and a metal precursor (MP).

[0061] The photosensitive polymer may include a first repeating unit comprising an ester group and a second repeating unit comprising an aryl group (AR). In FIG. 1, for convenience, the first repeating unit and the second repeating unit are depicted as forming a single repeating unit, but the present invention is not limited thereto. The first repeating unit and the second repeating unit may form a random copolymer or a block copolymer. Also, in FIG. 1, a protecting group (PG) is depicted as being included within the first repeating unit, but the present invention is not limited thereto, and the protecting group (PG) may be included within the second repeating unit.

[0062] Subsequently, when light, such as light with a wavelength of 13.5 nm, is irradiated onto the above photoresist composition, the PAG is converted into an acid while emitting secondary electrons. Additionally, the metal precursor (MP) also emits secondary electrons and is converted into a metal ion (M) as it separates from the ligand. Furthermore, the photosensitive polymer can be deprotected as some protecting groups dissociate due to the presence of the acid.

[0063] When baking is performed on the exposed photoresist composition after exposure, the deprotection of the photosensitive polymer is further accelerated. The ester group of the first repeating unit and the aryl group of the second repeating unit can form coordination bonds with the metal ion (M). In Type 1 of FIG. 1, an example is shown in which one ester group and one aryl group are each coordinated to one metal ion (M), and in Type 2, an example is shown in which two ester groups and two aryl groups are each coordinated to one metal ion (M). Since the number of ester groups and aryl groups coordinated to one metal ion (M) is two or more, a cross-linked structure can be obtained centered on the metal ion (M). Such a cross-linked structure can improve the resolution of the exposed photoresist composition.

[0064] quencher

[0065] The photoresist composition according to the embodiments of the technical concept of the present invention may further include a basic quencher.

[0066] The above basic quencher can serve to trap the acid in the non-exposed region when the acid generated from the PAG included in the photoresist composition according to the technical concept of the present invention diffuses into the non-exposed region of the photoresist film. By including the above basic quencher in the photoresist composition according to the technical concept of the present invention, problems caused by the acid generated in the exposed region of the photoresist film diffusing into the non-exposed region of the photoresist film after exposure of the photoresist film obtained from the photoresist composition can be prevented.

[0067] In exemplary embodiments, the basic quencher may consist of a primary aliphatic amine, a secondary aliphatic amine, a tertiary aliphatic amine, an aromatic amine, an amine containing a heterocyclic ring, a nitrogen-containing compound having a carboxyl group, a nitrogen-containing compound having a sulfonyl group, a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, amides, imides, carbamates, or ammonium salts. For example, the basic quencher is triethanolamine, triethylamine, tributylamine, tripropylamine, hexamethyl disilazan, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, N,N-bis(hydroxyethyl)aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, dimethylaniline, 2,6-diisopropylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, It may include N,N-dimethyltoluidine or combinations thereof, but is not limited to those exemplified above.

[0068] In other exemplary embodiments, the basic quencher may be composed of a photodegradable base. The photodegradable base may be composed of a compound that generates acid upon exposure and neutralizes the acid before exposure. The photodegradable base may lose its function of trapping the acid when degraded by exposure. Therefore, when a portion of a photoresist film formed from a chemically amplified photoresist composition containing a basic quencher composed of the photodegradable base is exposed, the photodegradable base loses its alkalinity in the exposed area of ​​the photoresist film, and the photodegradable base traps the acid in the unexposed area of ​​the photoresist film, thereby preventing the problem caused by the acid generated in the exposed area of ​​the photoresist film diffusing into the unexposed area of ​​the photoresist film.

[0069] The above photodegradable base may include a carboxylate or sulfonate salt of a photodegradable cation. For example, the above photodegradable cation may form a complex with an anion of a carboxylic acid having 1 to 20 carbon atoms. The above carboxylic acid may be, for example, formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexylcarboxylic acid, benzoic acid, or salicylic acid, but is not limited thereto.

[0070] In a photoresist composition according to embodiments of the technical concept of the present invention, the basic quencher may be included in an amount of about 0.01 weight% to about 5.0 weight% based on the total weight of the photoresist composition, but is not limited thereto.

[0071] Other ingredients

[0072] In exemplary embodiments, the photoresist composition according to embodiments of the technical concept of the present invention may further include at least one selected from a surfactant, a dispersant, a hygroscopic agent, and a coupling agent.

[0073] The surfactant may serve to improve the coating uniformity and wettability of the photoresist composition. In exemplary embodiments, the surfactant may be composed of, but is not limited to, sulfate esters, sulfonates, phosphate esters, soaps, amine salts, quaternary ammonium salts, polyethylene glycol, alkylphenolethylene oxide adducts, polyhydric alcohols, nitrogen-containing vinyl polymers, or combinations thereof. For example, the surfactant may include alkylbenzenesulfonates, alkylpyridinium salts, polyethylene glycol, or quaternary ammonium salts. When the photoresist composition contains the surfactant, the surfactant may be included in an amount of about 0.001% by weight to about 3% by weight based on the total weight of the photoresist composition.

[0074] The above-mentioned dispersant may serve to ensure that each component constituting the photoresist composition is uniformly dispersed within the photoresist composition. In exemplary embodiments, the dispersant may consist of, but is not limited to, epoxy resin, polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, glucose, sodium dodecyl sulfate, sodium citrate, oleic acid, linoleic acid, or a combination thereof. When the photoresist composition contains the dispersant, the dispersant may be included in an amount of about 0.001% by weight to about 5% by weight based on the total weight of the photoresist composition.

[0075] The above-mentioned hygroscopic agent may serve to prevent adverse effects caused by moisture in the photoresist composition. For example, the above-mentioned hygroscopic agent may serve to prevent the metal contained in the photoresist composition from being oxidized by moisture. In exemplary embodiments, the above-mentioned hygroscopic agent may be composed of polyoxyethylene nonylphenolether, polyethylene glycol, polypropylene glycol, polyacrylamide, or a combination thereof, but is not limited thereto. When the above-mentioned photoresist composition contains the above-mentioned hygroscopic agent, the above-mentioned hygroscopic agent may be included in an amount of about 0.001 weight% to about 10 weight% based on the total weight of the photoresist composition.

[0076] The coupling agent may serve to improve adhesion with the lower film when coating the photoresist composition onto the lower film. In exemplary embodiments, the coupling agent may include a silane coupling agent. The silane coupling agent may consist of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, or trimethoxy[3-(phenylamino)propyl]silane, but is not limited thereto. When the above photoresist composition includes the coupling agent, the coupling agent may be included in an amount of about 0.001 weight% to about 5 weight% based on the total weight of the above photoresist composition.

[0077] In a photoresist composition according to embodiments of the technical concept of the present invention, when the solvent consists only of an organic solvent, the photoresist composition may further include water. In this case, the water content in the photoresist composition may be about 0.001 weight% to about 0.1 weight%.

[0078] Manufacturing of integrated circuit devices

[0079] Next, a method for manufacturing an integrated circuit device using a photoresist composition according to the technical concept of the present invention will be described with specific examples.

[0080] FIG. 2 is a flowchart for explaining a method for manufacturing an integrated circuit device according to embodiments of the technical concept of the present invention. FIG. 3a to 3e are cross-sectional views illustrated in the order of process to explain a method for manufacturing an integrated circuit device according to embodiments of the technical concept of the present invention.

[0081] Referring to FIGS. 2 and FIGS. 3a, in process P10, a feature layer (110) is formed on a substrate (100), and in process P20, a photoresist film (130) is formed on the feature layer (110) using a photoresist composition according to the technical concept of the present invention.

[0082] The photoresist film (130) may include a metal precursor and a solvent, which are components of the photoresist composition according to the technical concept of the present invention. The more detailed composition of the photoresist composition is as described above.

[0083] The substrate (100) may include a semiconductor substrate. The feature layer (110) may be an insulating film, a conductive film, or a semiconductor film. For example, the feature layer (110) may be made of a metal, an alloy, a metal carbide, a metal nitride, a metal oxynitride, a metal oxycarbide, a semiconductor, polysilicon, an oxide, a nitride, an oxynitride, or a combination thereof, but is not limited thereto.

[0084] In exemplary embodiments, as illustrated in FIG. 3a, a bottom film (120) may be formed on the feature layer (110) before forming a photoresist film (130) on the feature layer (110). In this case, the photoresist film (130) may be formed on the bottom film (120). The bottom film (120) may serve to prevent adverse effects that the photoresist film (130) may receive from the lower feature layer (110). In exemplary embodiments, the bottom film (120) may be made of an organic or inorganic anti-reflective coating (ARC) material for a KrF excimer laser, an ArF excimer laser, an EUV laser, or any other light source. In exemplary embodiments, the bottom film (120) may be made of a bottom anti-reflective coating (BARC) film or a developable bottom anti-reflective coating (DBARC) film. In other exemplary embodiments, the bottom film (120) may comprise an organic component having an absorbing structure. The absorbing structure may be, for example, one or more benzene rings or a hydrocarbon compound having a structure in which benzene rings are fused. The bottom film (120) may be formed with a thickness of about 1 nm to about 100 nm, but is not limited thereto. In exemplary embodiments, the bottom film (120) may be omitted.

[0085] In order to form a photoresist film (130), a photoresist composition according to the technical concept of the present invention may be coated on a lower film (120). The coating may be performed by methods such as spin coating, spray coating, or dip coating. The thickness of the photoresist film (130) may be several tens to several hundred times the thickness of the lower film (120). The photoresist film (130) may be formed with a thickness of about 10 nm to about 1 μm, but is not limited thereto.

[0086] In process P30, a first bake may be performed on the photoresist film (130). The first bake may also be referred to as a post-apply bake (PAB).

[0087] The first bake may be performed at a temperature of about 80°C to about 140°C or about 90°C to about 120°C for about 10 seconds to about 100 seconds. If the temperature of the first bake is too low, the removal of the solvent may be insufficient. If the temperature of the first bake is too high, the resolution of the photoresist pattern may deteriorate.

[0088] Referring to FIG. 2 and FIG. 3b, in process P40, a first region (132), which is part of the photoresist film (130), is exposed to light so that the metal precursor in the first region (132) is separated from the ligand and converted into a metal ion while emitting secondary electrons.

[0089] In exemplary embodiments, to expose a first region (132) of a photoresist film (130), a photomask (140) having a plurality of light shielding areas (LS) and a plurality of light transmitting areas (LT) may be aligned at a predetermined position on the photoresist film (130), and the first region (132) of the photoresist film (130) may be exposed through the plurality of light transmitting areas (LT) of the photomask (140). To expose the first region (132) of the photoresist film (130), a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F2 excimer laser (157 nm), or an EUV laser (13.5 nm) may be used. In some embodiments, depending on the type of light source, a reflective photomask may be used instead of a transmissive photomask. Although the following description focuses on transmissive photomasks, those skilled in the art will understand that exposure can also be performed on reflective photomasks with an equivalent configuration.

[0090] The photomask (140) may include a transparent substrate (142) and a plurality of light-blocking patterns (144) formed in a plurality of light-blocking regions (LS) on the transparent substrate (142). The transparent substrate (142) may be made of quartz. The plurality of light-blocking patterns (144) may be made of chromium (Cr). A plurality of light-transmitting regions (LT) may be defined by the plurality of light-blocking patterns (144). According to the technical concept of the present invention, a reflective photomask for EUV exposure (not shown) may be used instead of the photomask (140) to expose the first region (132) of the photoresist film (130).

[0091] FIGS. 4a and FIGS. 4b are schematic diagrams for explaining EUV exposure performed on a photoresist film (130) on a feature layer (110).

[0092] Referring to FIG. 4a and FIG. 4b together, the EUV exposure apparatus (1000) may include an EUV light source (1100), an illumination optical system (1200), a photomask support (1300), a projection optical system (1400), and a substrate stage (1500).

[0093] The EUV light source (1100) can generate and output EUV light (EL) having high energy density. For example, the EUV light (EL) emitted from the EUV light source (1100) may have a wavelength of about 4 nm to 124 nm. In some embodiments, the EUV light (EL) may have a wavelength of about 4 nm to 20 nm, and the EUV light (EL) may have a wavelength of 13.5 nm.

[0094] The above EUV light source (1100) may be a plasma-based light source or a synchrotron radiation light source. Here, the plasma-based light source refers to a light source that generates plasma and utilizes light emitted by the plasma, and includes a laser-produced plasma light source or a discharge-produced plasma light source.

[0095] The above EUV light source (1100) may include a laser light source (1110), a transfer optical system (1120), a vacuum chamber (1130), a collector mirror (1140), a droplet generator (1150), and a droplet catcher (1160).

[0096] The laser light source (1110) may be configured to output a laser (OL). For example, the laser light source (1110) may output a carbon dioxide laser. The laser (OL) output from the laser light source (1110) may be introduced into the interior of the vacuum chamber (1130) by being incident on the window (1131) of the vacuum chamber (1130) through a plurality of reflective mirrors (1121, 1123) included in the transfer optical system (1120).

[0097] An aperture (1141) through which a laser (OL) can pass is formed in the center of the collector mirror (1140), and the laser (OL) can be introduced into the interior of the vacuum chamber (1130) through the aperture (1141) of the collector mirror (1140).

[0098] A droplet generator (1150) can generate a droplet that interacts with a laser (OL) to generate EUV light (EL) and can provide the droplet into the interior of a vacuum chamber (1130). The droplet may contain at least one of tin (Sn), lithium (Li), and xenon (Xe). For example, the droplet may contain at least one of tin (Sn), a tin compound (e.g., SnBr4, SnBr2, SnH), and a tin alloy (e.g., Sn-Ga, Sn-In, Sn-In-Ga).

[0099] The droplet collection unit (1160) is located below the droplet generator (1150) and may be configured to collect droplets that have not reacted with the laser (OL). Droplets provided from the droplet generator (1150) may react with the laser (OL) introduced into the vacuum chamber (1130) to generate EUV light (EL). The collector mirror (1140) may collect and reflect the EUV light (EL), thereby emitting the EUV light (EL) to an illumination optical system (1200) located outside the vacuum chamber (1130).

[0100] The illumination optical system (1200) includes a plurality of reflective mirrors and can transmit EUV light (EL) emitted from an EUV light source (1100) to an EUV photomask (PM). For example, the EUV light (EL) emitted from the EUV light source (1100) can be reflected by a reflective mirror within the illumination optical system (1200) and incident on an EUV photomask (PM) placed on a photomask support (1300).

[0101] An EUV photomask (PM) may be a reflective mask having a reflective region and a non-reflective (or intermediate reflective) region. The EUV photomask (PM) may include a reflective multilayer film formed on a mask substrate formed of a material having a low coefficient of thermal expansion, such as silicon (Si), and an absorption pattern formed on the reflective multilayer film. Here, the reflective multilayer film may correspond to a reflective region, and the absorption pattern may correspond to a non-reflective (or intermediate reflective) region.

[0102] The above EUV photomask (PM) reflects EUV light (EL) incident through the illumination optical system (1200) and directs it to the projection optical system (1400). Specifically, the EUV photomask (PM) structures the light incident from the illumination optical system (1200) into projection light based on the pattern shape formed by the reflection multilayer film and the absorption pattern on the mask substrate, and directs it to the projection optical system (1400). The projection light can be structured through at least a second-order diffraction order due to the EUV photomask (PM). This projection light is directed to the projection optical system (1400) while retaining information about the pattern shape of the EUV photomask (PM), and passes through the projection optical system (1400) to form an image corresponding to the pattern shape of the EUV photomask (PM) on the substrate (110).

[0103] The projection optical system (1400) may include a plurality of reflective mirrors (1410, 1430). Although two reflective mirrors (1410, 1430) are shown in the drawing within the projection optical system (1400), this is for convenience of explanation, and the projection optical system (1400) may include more reflective mirrors. For example, the projection optical system (1400) may generally include four to eight reflective mirrors. However, the number of reflective mirrors included in the projection optical system (1400) is not limited to the above figures.

[0104] A substrate (110) may be placed on a substrate stage (1500). The substrate stage (1500) may move in a first direction (X direction) and a second direction (Y direction) on an XY plane, and may also move in a third direction (Z direction) perpendicular to the XY plane. Due to the movement of the substrate stage (1500), the substrate (110) may also move in the same way in the first direction (X direction), the second direction (Y direction), and / or the third direction (Z direction).

[0105] When using EUV light, the light intensity required for exposure at a critical dimension uniformity (CDU) of 27 nm is approximately 25 mJ / cm² 2 Up to about 30 mJ / cm² 2 It is possible. That is, assuming other conditions are equal, an inverse relationship is established between the exposure light amount required for patterning to be performed normally and the CDU, and based on a 27 nm CDU, the photoresist composition according to the embodiments of the present invention is approximately 25 mJ / cm² 2 Up to about 30 mJ / cm² 2 A light intensity is required. This light intensity is significantly lower than that of conventional photoresist compositions that do not use metal precursors, which means that the exposure time is shorter and furthermore means that productivity is improved.

[0106] After exposing a first region (132) of the photoresist film (130) according to process P40, the photoresist film (130) may be baked a second time in process P50. The second baking may be referred to as a post-exposure bake (PEB). The second baking may be performed at a temperature of about 50°C to about 400°C for about 10 seconds to about 100 seconds, but is not limited thereto. In exemplary embodiments, during the second baking of the photoresist film (130), the degree of cross-linking between photosensitive polymer molecules in the first region (132) may be further increased. Accordingly, the difference in solubility to the developer between the exposed first region (132) and the unexposed second region (134) of the photoresist film (130) may be further increased, and pattern collapse may be prevented.

[0107] Specifically, by the second bake, the phenomenon of cross-linking in which the photosensitive polymer coordinately bonds to the metal ions occurs extensively, thereby forming macromolecules that are difficult to remove by the developer. Although the present invention is not limited by any specific theory, the mechanism of cross-linking in which the photosensitive polymer coordinately bonds to metal ions is described above with reference to FIG. 1 and is further explained in more detail with a more specific example with reference to FIG. 5.

[0108] Figure 5 is a schematic diagram illustrating an exemplary process in which a photosensitive polymer is crosslinked by a metal precursor.

[0109] Referring to FIG. 5, poly(hydroxystyrene-r-isopropylcyclopentyl methacrylate) is provided as a photosensitive polymer, and tin(II) 2-ethylhexanoate is provided as a metal precursor. The photosensitive polymer has a first repeating unit comprising isopropylcyclopentyl methacrylate and a second repeating unit comprising hydroxystyrene. The hydroxystyrene may comprise one, two, or three or more hydroxyl groups. In FIG. 5, a, representing the number of hydroxyl groups, is any integer from 1 to 5.

[0110] By EUV lithography, ligands are removed from the metal precursor, Sn 2+ Ions are generated, and the isopropylcyclopentyl group, a protecting group of the photosensitive polymer, is separated from the ester group by acid. The photosensitive polymer molecules Sn 2+ It can form coordinate bonds with ions in various ways.

[0111] As seen in 1) of Fig. 5, the oxygen atoms of the deprotected ester group together with the oxygen atoms of the deprotected ester group of another molecule or segment Sn 2+ Forming coordinate bonds with ions, or, as seen in 2), the oxidation atoms of the deprotected ester group together with the oxygen atoms of hydroxystyrene of other molecules or segments of Sn 2+ Forming coordinate bonds with ions, and / or, as seen in 3), the oxygen atoms of hydroxystyrene together with the oxygen atoms of hydroxystyrene of other molecules or segments of Sn 2+ It can form coordinate bonds with ions.

[0112] In this way, the metal precursors in the exposed first region (132) are converted into metal ions, causing the photosensitive polymers to cross-link with each other to form macromolecules, while the metal precursors in the unexposed second region (134) remain in their state, so the photosensitive polymers do not cross-link with each other. Consequently, a difference in solubility arises between the cross-linked macromolecules and the uncross-linked photosensitive polymer molecules.

[0113] Referring to FIG. 2 and FIG. 3c, in process P60, a photoresist film (130) is developed using a developer to remove a second region (134) of the photoresist film (130). As a result, a photoresist pattern (130P) consisting of an exposed first region (132) of the photoresist film (130) can be formed.

[0114] The photoresist pattern (130P) may include a plurality of openings (OP). After the photoresist pattern (130P) is formed, the portion exposed through the plurality of openings (OP) of the lower film (120) can be removed to form a lower pattern (120P).

[0115] In exemplary embodiments, the development of the photoresist film (130) can be performed by a negative-tone development (NTD) process. At this time, n-butyl acetate or 2-heptanone may be used as the developer, but the type of developer is not limited to these.

[0116] As described with reference to FIG. 3b, as the difference in solubility to the developer between the exposed first region (132) and the unexposed second region (134) in the photoresist film (130) increases, the first region (132) may remain intact without being removed while the photoresist film (130) is developed to remove the second region (134) in the process of FIG. 3c. Therefore, after developing the photoresist film (130), residual defects such as footing do not occur, and a vertical sidewall profile can be obtained in the photoresist pattern (130P). In this way, by improving the profile of the photoresist pattern (130P), the critical dimensions of the intended processing area in the feature layer (110) can be precisely controlled when processing the feature layer (110) using the photoresist pattern (130P).

[0117] Referring to FIGS. 2 and FIGS. 3d, in process P70, a feature layer (110) is processed using a photoresist pattern (130P) from the result of FIG. 3c.

[0118] In order to process the feature layer (110), various processes can be performed, such as etching the feature layer (110) exposed through the opening (OP) of the photoresist pattern (130P), implanting impurity ions into the feature layer (110), forming an additional film on the feature layer (110) through the opening (OP), and deforming a part of the feature layer (110) through the opening (OP). FIG. 9d illustrates an exemplary process for processing the feature layer (110) in which the feature layer (110) exposed through the opening (OP) is etched to form a feature pattern (110P).

[0119] In other exemplary embodiments, the process of forming the feature layer (110) in the process described with reference to FIG. 3a may be omitted, and in this case, the substrate (100) may be processed using a photoresist pattern (130P) instead of the process P70 of FIG. 2 and the process described with reference to FIG. 3d. For example, various processes may be performed using the photoresist pattern (130P), such as etching a portion of the substrate (100), implanting impurity ions into a portion of the substrate (100), forming an additional film on the substrate (100) through an opening (OP), and deforming a portion of the substrate (100) through an opening (OP).

[0120] Referring to FIG. 3e, the photoresist pattern (130P) and the lower pattern (120P) remaining on the feature pattern (110P) in the result of FIG. 3d can be removed. An ashing and stripping process may be used to remove the photoresist pattern (130P) and the lower pattern (120P).

[0121] According to the method for manufacturing an integrated circuit device based on the technical concept of the present invention described with reference to FIGS. 2 and FIGS. 3a to 3e, secondary electrons are generated not only in the PAG by exposure but also in the metal precursor, so the protection device can be deprotected more quickly. Consequently, the amount of light required for an equivalent level of exposure is reduced, resulting in a reduction in the time required for exposure and an improvement in productivity. Furthermore, since the moiety of the photosensitive polymer is coordinately bonded to the metal ions derived from the metal precursor to form a cross-linked structure, the contrast (i.e., resolution) of the pattern can be significantly improved. Moreover, since the metal ions remain within the photoresist pattern, the etch resistance of the photoresist pattern can be improved when anisotropic etching is performed.

[0122] The structure and effects of the present invention will be explained in more detail below with specific examples and comparative examples, but these examples are merely intended to provide a clearer understanding of the present invention and are not intended to limit the scope of the present invention.

[0123] <Examples 1 to 3>

[0124] A photoresist composition comprising poly(3,4-dihydroxystyrene-r-isopropylcyclopentyl methacrylate) as a photosensitive polymer, triphenylsulfonium difluoroalkylsulfonate as a PAG, and tin(II) 2-ethylhexanoate as a metal precursor was prepared by varying the content of the metal precursor.

[0125] <Examples 4 to 6>

[0126] A photoresist composition comprising poly(monohydroxystyrene-r-isopropylcyclopentyl methacrylate) as a photosensitive polymer, triphenylsulfonium difluoroalkylsulfonate as a PAG, and tin(II) 2-ethylhexanoate as a metal precursor was prepared by varying the content of the metal precursor.

[0127] <Comparative Example 1>

[0128] A photoresist composition was prepared in the same manner as in Example 1, except that no metal precursor was added.

[0129] <Comparative Example 2>

[0130] A photoresist composition was prepared in the same manner as in Example 1, except for the content of the metal precursor.

[0131] After applying each photoresist composition of Examples 1 to 3, Comparative Example 1, and Comparative Example 2 onto a substrate, EUV exposure was performed using an ASML NXE3350 instrument to form a pillar pattern, and after developing with n-butyl acetate, the results were analyzed and summarized in Table 1 below. Both PAB and PEB were performed at 100°C for 60 seconds.

[0132] [Table 1]

[0133]

[0134] As shown in Table 1, it was confirmed that the photoresist pattern was not formed well when 15 wt% of the metal precursor was added. In addition, it was confirmed that when 5 wt% to 10 wt% of the metal precursor was added, the photoresist pattern was formed well with a smaller amount of exposure compared to when no metal precursor was added. This means that the exposure time is proportionally shorter, which is directly related to increased productivity.

[0135] <Comparative Example 3>

[0136] Patterning of the photoresist material film was attempted in the same manner as in Example 1, except that the PAB temperature was changed to 150℃.

[0137] [Table 2]

[0138]

[0139] As shown in Table 2, it was confirmed that in the case of Example 1, a photoresist pattern was formed well even with a significantly smaller exposure amount compared to Comparative Example 1. On the other hand, in the case of Comparative Example 3, it was confirmed that a photoresist pattern was not formed well even though only the PEB temperature was changed to 150 ℃ compared to Example 1 (i.e., even though 5 wt% of the metal precursor was added as in Example 1).

[0140] As shown in Tables 1 and 2, it was confirmed that the content of the metal precursor and the temperature at which PAB is performed affect the formation of the photoresist pattern.

[0141] The thickness after patterning (i.e., thickness immediately after development) using the photoresist compositions of Example 1 and Comparative Example 1 was measured for each exposure dose, and the remaining percentage was calculated in comparison to the thickness of the initially applied material film, and the results are shown in FIG. 6.

[0142] Referring to FIG. 6, it was confirmed that the photoresist composition of Example 1 exhibits an exposure effect and forms a residual film even at a significantly lower exposure dose compared to the photoresist composition of Comparative Example 1.

[0143] In addition, after a sufficient exposure dose for patterning was secured, the pattern prepared with the photoresist composition of Comparative Example 1 showed a residual thickness ratio of 50% or more and less than 60%. On the other hand, the pattern prepared with the photoresist composition of Example 1 showed a residual thickness ratio of more than 60%. Therefore, it can be seen that the photoresist composition of Example 1 has superior etching resistance compared to the photoresist composition of Comparative Example 1.

[0144] As described above, although embodiments of the present invention have been described in detail, a person skilled in the art to which the present invention pertains will be able to modify and implement the present invention in various ways without departing from the spirit and scope of the present invention as defined in the appended claims. Therefore, future modifications to the embodiments of the present invention will not depart from the technology of the present invention. Explanation of the symbols

[0145] 100: Substrate, 110: Feature layer, 130: Photoresist film, 130P: Photoresist pattern, 132: First region, 134: Second region.

Claims

Claim 1 A photoresist composition comprising: a photosensitive polymer having a protecting group and a polydispersity index (PI) of 1 to 3; a photoacid generator (PAG); a metal precursor comprising a metal alkoxide capable of generating metal ions and secondary electrons upon irradiation with light of 13.5 nm and having a structure in which an organic ligand is coordinately bonded to a metal atom; and a solvent, wherein the photoacid generator is included in an amount of 30% to 40% by weight based on the total weight of the photosensitive polymer. Claim 2 delete Claim 3 A photoresist composition according to claim 1, wherein the metal precursor comprises at least one of tin (II) ethoxide, tin (IV) n-butoxide, tin (IV) tert-butoxide, and titanium (IV) isopropoxide, and the content of the metal precursor in the photoresist composition is 2% to 10% by weight. Claim 4 A photoresist composition according to claim 3, characterized in that the content of the metal precursor in the photoresist composition is 3% to 7.5% by weight. Claim 5 delete Claim 6 A photoresist composition according to claim 1, characterized in that the protecting group is an acid-labile protecting group that can be separated from the photosensitive polymer by acid. Claim 7 A photoresist composition comprising: a photosensitive polymer having a protecting group and a polydispersity index (PI) of 1 to 3; a photoacid generator (PAG) capable of generating acid upon irradiation with light of 13.5 nm; a metal precursor capable of generating metal ions and secondary electrons upon irradiation with light of 13.5 nm, having a structure in which an organic ligand is coordinately bonded to a metal atom, and having a structure of the following chemical formula (I); and a solvent; wherein the photoacid generator is included in an amount of 30% to 40% by weight based on the total weight of the photosensitive polymer. n L m (I)(where M is the atomic absorption cross-section for light irradiation of 13.5 nm, 5x10 6 cm 2 / mol or more of a metallic element, where L is an alkoxy group having 2 to 12 carbon atoms, n is an integer from 1 to 12, and m is an integer from 2 to 72, which is an integer from 2n to 6n) Claim 8 A photoresist composition according to claim 7, wherein the metal element M is selected from tellurium (Te), titanium (Ti), lead (Pb), gold (Au), silver (Ag), cesium (Cs), bismuth (Bi), tin (Sn), zinc (Zn), antimony (Sb), and indium (In), and n is 1. Claim 9 A photoresist composition according to claim 7, characterized in that the metal element M is Sn and the content of the metal precursor is 2% to 10% by weight relative to the total weight of the photoresist composition. Claim 10 In claim 7, L is methyl, methoxy, ethyl, ethoxy, isopropyl, isopropoxy, n-butyl, n-butoxy, t-butyl, t-butoxy, acetate, 2-methylpentanoate, 2-ethylpentanoate, 2-methylhexanoate, 2-ethylhexanoate, 3-methylpentanoate, 3-ethylpentanoate, 3-methylhexanoate, 3-ethylhexanoate, 4-methylpentanoate, 4-methylhexanoate, 4-ethylhexanoate, 2,3-dimethylpentanoate, 2,3-dimethylhexanoate, 2,3-diethylpentanoate, 2,3-diethylhexanoate, A photoresist composition characterized by being 2-ethyl-3-methylpentanoate, 2-methyl-3-ethylpentanoate, 2-ethyl-3-methylhexanoate, or 2-methyl-3-ethylhexanoate. Claim 11 A photoresist composition according to claim 7, wherein the photosensitive polymer comprises an ester group within a first repeating unit, and the protecting group is bonded to the ester group. Claim 12 A photoresist composition according to claim 11, characterized in that, in the presence of acid, the protecting group is separated from the ester group and the ester group is configured such that it forms a coordination bond with the metal element M. Claim 13 A photoresist composition according to claim 11, wherein the photosensitive polymer further comprises a second repeating unit comprising a hydroxyl group or a carboxyl group, and wherein the second repeating unit is configured such that the hydroxyl group or the carboxyl group forms a coordination bond with the metal element M in the presence of an acid. Claim 14 A photoresist composition according to claim 13, wherein the second repeating unit comprises one or more of the moiety listed in the following chemical formula (II). (II)(Here, "*" indicates the joining position) Claim 15 A photoresist composition according to claim 7, further comprising 0.01% to 5% by weight of a basic quencher based on the total weight of the photoresist composition. Claim 16 A photoresist composition comprising: a photosensitive polymer having a polydispersity index (PI) of 1 to 3; a photogenerator; a metal precursor having a structure in which an organic ligand is coordinately bonded to a metal atom and having tin(II) ethoxide, and included in an amount of 3% to 7.5% by weight based on the total weight of the photosensitive polymer; a basic quencher; and a solvent; wherein the photogenerator is included in an amount of 30% to 40% by weight based on the total weight of the photosensitive polymer.

Images