Photoresist composition and method of manufacturing semiconductor device using same

Abstract

The present disclosure provides a photoresist composition and a method of manufacturing a semiconductor device using the same. The method of manufacturing a semiconductor device includes forming a first resist layer on a substrate, forming a second resist layer on the first resist layer, exposing a first region of the second resist layer, forming a photoresist pattern by performing a heat treatment on the second resist layer to remove an unexposed second region of the second resist layer, and forming a second region of the second resist layer. And processing the first resist layer using the photoresist pattern.

Description

Technical Field

[0001] The example embodiments relate to photoresist compositions and methods for manufacturing semiconductor devices using the photoresist compositions. Background Technology

[0002] Advances in electronic technology have led to rapid development in the miniaturization of semiconductor devices. This miniaturization requires photolithography processes capable of forming micropatterns.

[0003] Photolithography typically includes exposure and development processes. During exposure, light of a specific wavelength is shone onto the photoresist layer to cause changes in its chemical structure. The development process utilizes the solubility difference between exposed and unexposed areas of the photoresist layer, using a developer to selectively remove either the exposed or unexposed areas.

[0004] As the patterns formed in the photolithography process become more refined, the photoresist patterns are more prone to collapse or loss due to the developer during the development process. Summary of the Invention

[0005] Example embodiments provide a photoresist composition and a method of manufacturing a semiconductor device using the photoresist composition, the photoresist composition reducing or preventing defects caused by collapse of the photoresist pattern and residues of the photoresist layer during development in a photolithography process.

[0006] The example embodiment provides a method for manufacturing semiconductor devices with simplified processes and increased productivity.

[0007] According to an example embodiment, a method of manufacturing a semiconductor device includes: forming a first resist layer on a substrate, forming a second resist layer on the first resist layer, exposing a first region of the second resist layer, forming a photoresist pattern by performing a heat treatment on the second resist layer to remove an unexposed second region of the second resist layer, and processing the first resist layer using the photoresist pattern.

[0008] According to an example embodiment, a method of manufacturing a semiconductor device includes: forming a first photoresist layer on a substrate; forming a second photoresist layer on the first photoresist layer; exposing a first region of the second photoresist layer; performing a heat treatment on the second photoresist layer to form a photoresist pattern; and processing an underlying layer using the photoresist pattern. Forming the photoresist pattern may include performing a first heat treatment at a temperature of 110°C to 180°C to crosslink the first region and the first photoresist layer, and performing a second heat treatment at a temperature of 200°C to 280°C to remove an unexposed second region of the second photoresist. The second photoresist layer may include an organometallic compound, additives, and a solvent. The organometallic compound may include two or more hydrocarbon groups covalently bonded to a metal and one or more halogen groups F, Cl, Br, or I covalently bonded to the metal. The metal may be polonium (Po), tellurium (Te), titanium (Ti), lead (Pb), gold (Au), silver (Ag), cesium (Cs), bismuth (Bi), tin (Sn), hafnium (Hf), zinc (Zn), cobalt (Co), aluminum (Al), antimony (Sb), indium (In), cadmium (Cd), or astatine (At). The hydrocarbon groups may each be independently substituted or unsubstituted C1 to C12 alkyl groups, substituted or unsubstituted C5 to C8 cycloalkyl groups, or substituted or unsubstituted C6 to C14 aryl groups. In some embodiments, the boiling point of the organometallic compound may be higher than the temperature at which the first heat treatment is performed and lower than the temperature at which the second heat treatment is performed.

[0009] According to an example embodiment, the photoresist composition includes an organometallic compound, additives, and a solvent. The organometallic compound may include tetravalent tin (Sn) as a central metal atom, two or more hydrocarbon groups covalently bonded to tin, and one or more halogen groups F, Cl, Br, or I covalently bonded to tin. The hydrocarbon groups may each be independently substituted or unsubstituted C1 to C12 alkyl groups, substituted or unsubstituted C5 to C8 cycloalkyl groups, or substituted or unsubstituted C6 to C14 aryl groups. Attached Figure Description

[0010] Figure 1 This is a flowchart illustrating a method for manufacturing a semiconductor device according to an example embodiment.

[0011] Figure 2 This is a flowchart illustrating a method for manufacturing a semiconductor device according to an example embodiment.

[0012] Figure 3 This is a top view illustrating a method for manufacturing a semiconductor device according to an example embodiment.

[0013] Figures 4A to 4E It corresponds to Figure 3The diagram shows a cross-sectional view along line A-A' and illustrates a method for manufacturing a semiconductor device according to an example embodiment. Detailed Implementation

[0014] This disclosure can be modified in various ways and can have various embodiments, among which specific embodiments will be described in detail with reference to the accompanying drawings. However, it should be understood that the description of specific embodiments of this disclosure is not intended to limit this disclosure to a particular mode of practice, and this disclosure is intended to cover all modifications, equivalents, and substitutions included within the spirit and technical scope of this disclosure.

[0015] In this disclosure, the term "substituted" means that the hydrogen atom is substituted with a deuterium, halogen group, hydroxyl group, amino group, substituted or unsubstituted C1 to C30 amino group, nitro group, substituted or unsubstituted C1 to C40 silyl group, C1 to C30 alkyl group, C1 to C10 haloalkyl group, C1 to C10 alkylsilyl group, C3 to C30 cycloalkyl group, C6 to C14 aryl group, C1 to C20 alkoxy group, or nitrile group. The term "unsubstituted" means that the hydrogen atom remains unchanged and is not substituted with any substituent.

[0016] In this disclosure, unless otherwise defined, the term "alkyl" refers to a straight-chain or branched aliphatic hydrocarbon group. An alkyl group can be a "saturated alkyl" group without double or triple bonds. An alkyl group can be C1 to C20 alkyl. For example, an alkyl group can be C1 to C10 alkyl or C1 to C6 alkyl. For example, C1 to C4 alkyl refers to an alkyl chain having 1 to 4 carbon atoms, and can refer to a selection from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl (t-butyl). For example, an alkyl group can refer to methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, or hexyl.

[0017] In this disclosure, unless otherwise defined, the term "cycloalkyl" may refer to a monovalent cyclic aliphatic hydrocarbon group.

[0018] In this disclosure, the term "aryl" refers to a substituent in which all atoms of the cyclic substituent have p orbitals and these p orbitals are conjugated. Aryl groups can include monocyclic or polycyclic (e.g., rings sharing adjacent carbon atom pairs) functional groups.

[0019] In this disclosure, unless otherwise defined, the term "halogen group" may refer to a fluorine (F), chlorine (Cl), bromine (Br) or iodine (I) functional group.

[0020] The example embodiments relate to photoresist compositions and methods for forming photolithographic patterns using the photoresist compositions. In the example embodiments, a method for forming patterns using photolithography can be employed during the manufacture of semiconductor devices. Therefore, the following description is provided in the context of methods for manufacturing semiconductor devices.

[0021] The photoresist composition according to the example embodiments will be described in detail below, followed by a method of manufacturing a semiconductor device using the photoresist composition.

[0022] The photoresist composition according to the example embodiments may include organometallic compounds, additives, and solvents.

[0023] The organometallic compound according to the example embodiment can be an organic compound having a structure in which a carbon (C) functional group is bonded to a central metal atom.

[0024] In an example embodiment, the organometallic compound may be a photosensitive material that can induce a photochemical reaction when irradiated by a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F2 excimer laser (157 nm), or extreme ultraviolet (EUV) light (13.5 nm).

[0025] In example embodiments, organometallic compounds can be used as non-chemically amplified photoresist materials. For instance, in a photolithography process, organometallic compounds can be materials that form photoresist patterns directly after the exposure process without undergoing a chemical amplification reaction via a catalyst. For example, organometallic compounds may not exhibit chemical amplification.

[0026] In the example embodiments, the central metal atom of the organometallic compound may be a metal with significant EUV absorption, such as polonium (Po), tellurium (Te), titanium (Ti), lead (Pb), gold (Au), silver (Ag), cesium (Cs), bismuth (Bi), tin (Sn), hafnium (Hf), zinc (Zn), cobalt (Co), aluminum (Al), antimony (Sb), indium (In), cadmium (Cd), or astatine (At), but the example embodiments are not limited to these.

[0027] In an example embodiment, the central metal atom of the organometallic compound may be tetravalent tin (Sn). Tin (Sn) strongly absorbs 13.5 nm EUV light, allowing tin-containing organometallic compounds to exhibit enhanced sensitivity to high-energy light. Therefore, the organometallic compound according to the example embodiment may include tin as the central atom, resulting in enhanced photosensitivity.

[0028] In example embodiments, organometallic compounds may have a structure in which an organic functional group and a halogen group are covalently bonded to a central metal atom. Organometallic compounds may include, for example, a metal as a central atom, two or more hydrocarbon groups covalently bonded to the metal, and one or more halogen groups covalently bonded to the metal. The hydrocarbon groups may each be independently substituted or unsubstituted C1 to C12 alkyl, substituted or unsubstituted C5 to C8 cycloalkyl, or substituted or unsubstituted C6 to C14 aryl, and the halogen group may be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0029] In example embodiments, organometallic compounds may include compounds represented by the following chemical formula 1.

[0030] Chemical Formula 1 .

[0031] In chemical formula 1, R 1 and R 2 Each is independently a substituted or unsubstituted C1 to C12 alkyl, a substituted or unsubstituted C5 to C8 cycloalkyl, or a substituted or unsubstituted C6 to C14 aryl, and X 1 and X 2 Each is independently one of the halogen groups F, Cl, Br or I.

[0032] Compounds represented by Formula 1 may include tetravalent tin (Sn) as a central metal atom, two hydrocarbon groups covalently bonded to tin, and two halogen groups covalently bonded to tin. The hydrocarbon groups may each be independently substituted or unsubstituted C1 to C12 alkyl, substituted or unsubstituted C5 to C8 cycloalkyl, or substituted or unsubstituted C6 to C14 aryl, and the halogen groups may be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0033] For example, organometallic compounds may include at least one selected from the following: .

[0034] In an example embodiment, the three hydrocarbon groups may be covalently bonded to a single central metal atom of the organometallic compound. For example, the organometallic compound may include a compound represented by the following chemical formula 2.

[0035] Chemical formula 2 .

[0036] In chemical formula 2, R 3 To R 5Each is independently a substituted or unsubstituted C1 to C12 alkyl, a substituted or unsubstituted C5 to C8 cycloalkyl, or a substituted or unsubstituted C6 to C14 aryl, and X 3 It is one of the halogen groups F, Cl, Br or I.

[0037] In an example embodiment, the organometallic compound can be a photosensitive material that is exposed to light and breaks down using a chain-breaking mechanism. For example, when the organometallic compound is exposed to light of a specific wavelength, tin (Sn) in formula 1 reacts with R... 1 and / or R 2 The bonds between tin (Sn) and R can break. 1 and / or R 2 The bond dissociation energy between them can be lower than that between tin (Sn) and X. 1 and / or X 2 The bond dissociation energy between them. Therefore, when organometallic compounds are exposed to a higher bond energy than tin (Sn) and R, the bond dissociation energy is higher. 1 and / or R 2 The bond dissociation energy between them is lower than that between tin (Sn) and X. 1 and / or X 2 When the wavelength intensity of light is the same as the bond dissociation energy between tin (Sn) and R, only tin (Sn) and R... 1 and / or R 2 The bond can be broken, and in chemical formula 1, tin (Sn) reacts with X. 1 and / or X 2 The bonds between tin (Sn) and R remain unchanged. This principle allows for the selective breaking of the bonds between tin (Sn) and R. 1 and / or R 2 The key between them.

[0038] Similarly, when organometallic compounds are exposed to light of a specific wavelength, the central metal atom in Formula 2 reacts with the R atom in Formula 2. 3 R 4 and / or R 5 The bonds between them can be selectively broken.

[0039] In example embodiments, the organometallic compound may include a photopolymer. For example, the photopolymer may be a homopolymer comprising a plurality of individual monomers. For example, the photopolymer may be a homopolymer comprising a monomer of Formula 1 or a monomer of Formula 2. Furthermore, the individual monomer may be an acrylate-based monomer.

[0040] In exemplary embodiments, the photopolymer may be a copolymer comprising two or more monomers. For example, the photopolymer may be a copolymer formed by polymerizing at least one monomer of Formula 1 and at least one monomer of Formula 2. Furthermore, the two or more monomers may each be independently selected from acrylate-based monomers or styrene-based monomers. The photopolymer may be, for example, polymethyl methacrylate (PMMA), or a copolymer of α-chloromethyl methacrylate and α-methylstyrene.

[0041] In the photoresist composition according to the example embodiment, based on 100 wt% of the photoresist composition, the organometallic compound may be included in an amount from about 0.1 wt% to about 90 wt%, or any range therewith (e.g., about 40 wt% to about 95 wt%, about 45 wt% to about 90 wt%, or about 50 wt% to about 90 wt%).

[0042] In an example embodiment, the photoresist composition may include additives. Additives may include various types of substances and enhance the physical and chemical properties of the photoresist, thereby enabling the formation of stable and finer photoresist patterns.

[0043] In example embodiments, the additive may include at least one selected from crosslinking agents, surfactants, dispersants, hygroscopic agents, coupling agents, leveling agents, and organic acids.

[0044] Crosslinking agents can enhance the crosslinking between organometallic compounds and binders during polymerization via heat treatment. When crosslinking agents are used, the physical properties of the crosslinked polymer can vary depending on the presence or absence of the crosslinking agent, its type, or its content. For example, the etching rate of a crosslinked polymer can vary depending on the presence or absence of the crosslinking agent, its type, or its content.

[0045] The crosslinking agent may be selected from at least one of polyfunctional (meth)acrylates, cyclic ether compounds, glycol urils, diisocyanates, melamine, benzomelamine, polynuclear phenols, polyfunctional thiols, polysulfides, and sulfides, but the examples are not limited thereto.

[0046] Polyfunctional (meth)acrylates can be compounds having two or more (meth)acryloyl groups. Polyfunctional (meth)acrylates can include, for example, polyfunctional (meth)acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, epoxide-modified polyfunctional (meth)acrylates, polyfunctional urethane (meth)acrylates obtained by reacting a (meth)acrylate with a hydroxyl group (-OH) with a polyfunctional isocyanate, or carboxyl-containing polyfunctional (meth)acrylates obtained by reacting a (meth)acrylate with a hydroxyl group with an acid anhydride.

[0047] When the photoresist composition according to the example embodiment contains a crosslinking agent, the crosslinking agent may be included in an amount of 1 to 60 parts by weight, or any range thereof (e.g., 2 to 50 parts by weight or 3 to 40 parts by weight) based on 100 parts by weight of the organometallic compound, but the example embodiment is not limited thereto.

[0048] Surfactants can improve the coating uniformity and wettability of photoresist compositions. In exemplary embodiments, surfactants may include sulfate salts, sulfonates, phosphate esters, soapstones, amine salts, quaternary ammonium salts, polyethylene glycol, alkylphenol ethoxylated adducts, polyols, nitrogen-containing vinyl polymers, or combinations thereof, but the exemplary embodiments are not limited thereto.

[0049] Surfactants can be, for example, selected from fluoroalkylbenzenesulfonates, fluoroalkyl carboxylates, fluoroalkyl polyoxyethylene ethers, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonates, and diglycerintetrakis(fluoroalkyl polyoxyethylene) The following are at least one of the following: ethers), fluoroalkyl trimethylammonium salt, fluoroalkyl aminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, and alkyl diphenyl ether disulfonate, but the exemplary embodiments are not limited thereto.

[0050] When the photoresist composition according to the example embodiment contains a surfactant, the surfactant may be included in an amount of 0.001 parts by weight to 1 part by weight, or any range thereof (e.g., 0.001 parts by weight to 0.1 parts by weight or 0.01 parts by weight to 0.1 parts by weight) based on 100 parts by weight of the organometallic compound, but the example embodiment is not limited thereto.

[0051] Dispersants can be used to uniformly disperse each component of a photoresist composition within the photoresist composition. In exemplary embodiments, dispersants may include epoxy resins, polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, glucose, sodium lauryl sulfate, sodium citrate, oleic acid, linoleic acid, or combinations thereof, but the exemplary embodiments are not limited thereto.

[0052] When the photoresist composition according to the example embodiment includes a dispersant, the dispersant may be included in an amount ranging from about 0.001 wt% to about 5 wt% or any range thereof, based on 100 wt% of the photoresist composition.

[0053] Desiccant can be used to prevent adverse effects caused by moisture in the photoresist composition. For example, a desiccant can be used to prevent the metals included in the photoresist composition from being oxidized by moisture. In exemplary embodiments, the desiccant may include polyoxyethylene nonylphenyl ether, polyethylene glycol, polypropylene glycol, polyacrylamide, or combinations thereof, but the exemplary embodiments are not limited thereto.

[0054] When the photoresist composition according to the example embodiment includes a hygroscopic agent, the hygroscopic agent may be included in an amount ranging from about 0.001 wt% to about 10 wt% or any range thereof, based on 100 wt% of the photoresist composition.

[0055] The coupling agent can be an adhesion promoter used to improve the adhesion between the photoresist layer and the substrate. For example, the coupling agent can be used to improve the adhesion to the substrate when the photoresist composition is coated on the substrate. In an exemplary embodiment, the coupling agent may include a silane coupling agent. The coupling agent may be, for example, a silane coupling agent. More specifically, the silane coupling agent may be vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 1,p-styrenetrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 2, or trimethoxy[3-(phenylamino)propyl]silane, but the exemplary embodiments are not limited thereto.

[0056] When the photoresist composition according to the example embodiment includes a coupling agent, the coupling agent may be included in an amount ranging from about 0.001 wt% to about 5 wt% or any range thereof, based on 100 wt% of the photoresist composition.

[0057] Leveling agents are substances used to improve the smoothness of a coating during printing. Any known leveling agent that is commercially available can be used as a leveling agent.

[0058] The organic acid may be p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, fluorinated sulfonate, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or combinations thereof, but the example embodiments are not limited thereto.

[0059] The solvent included in the photoresist composition according to the example embodiments may include an organic solvent. The organic solvent may include at least one of ethers, alcohols, glycol ethers, aromatic hydrocarbons, ketones, and esters, but the example embodiments are not limited thereto.

[0060] For example, organic solvents can be 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, isopropanol, isobutanol, 4-methyl-2-pentanol (methyl isobutyl methanol: 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, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate. 2-hydroxy-2-methylpropionate), ethyl ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, γ-butyrolactone, methyl 2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate, or combinations thereof. Solvents may be used alone or in combination of at least two different types.

[0061] In the photoresist composition according to the example embodiment, when the solvent consists only of organic solvents, the photoresist composition may also include water. Based on 100 wt% of the photoresist composition, the water content in the photoresist composition may be from about 0.001 wt% to about 0.1 wt%, or any range thereof.

[0062] In the photoresist composition according to the example embodiment, the solvent content may be the remaining amount in addition to the content of major components such as organometallic compounds.

[0063] According to example embodiments, the photoresist composition may include any component within the scope that does not impair the effects of this disclosure. When the photoresist composition includes components such as any component (e.g., resin, alkaline quencher, or additive), the solvent content may be the remainder in addition to the content of the main component and any component. For example, based on 100 wt% of a photoresist composition, the solvent may be included in an amount from about 0.1 wt% to about 99 wt%, or any range thereof.

[0064] In example embodiments, the photoresist composition may also include a basic quencher.

[0065] Alkaline quenchers can control the balance of acidic and alkaline substances in photoresist compositions. For example, alkaline quenchers can inhibit the diffusion of acids in the photoresist composition and unwanted chemical reactions between metal elements and organic compounds. Therefore, the structural stability of organometallic compounds in the photoresist composition can be maintained.

[0066] In example embodiments, the alkaline quencher may include primary fatty amines, secondary fatty amines, tertiary fatty amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, nitrogen-containing alcohols, amides, imides, carbamates, or ammonium salts. Alkaline quenchers may include, for example, triethanolamine, triethylamine, tributylamine, tripropylamine, hexamethyldisilazane, 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, N,N-dimethyltoluidine, or combinations thereof, but the exemplary embodiments are not limited thereto.

[0067] In the photoresist composition according to the example embodiment, based on 100 wt% of the photoresist composition, an alkaline quencher may be included in an amount from about 0.01 wt% to about 5.0 wt%, or any range thereof, but the example embodiment is not limited thereto.

[0068] The photoresist composition described above can be used in the manufacture of semiconductor devices. For example, the photoresist composition can be used to manufacture integrated circuit devices that require the formation of high aspect ratio patterns. The photoresist composition can be used, for example, to manufacture semiconductor memory devices for forming micropatterns with widths of 5 nm to 100 nm, or any range therewith, such as micropatterns with widths of 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, or 5 nm to 20 nm.

[0069] The following describes a method for manufacturing semiconductor devices using a photoresist composition.

[0070] Figure 1 This is a flowchart illustrating a method for manufacturing a semiconductor device according to an example embodiment. Figure 2 This is a flowchart illustrating a method for manufacturing a semiconductor device according to an example embodiment. Figure 3 This is a top view illustrating a method for manufacturing a semiconductor device according to an example embodiment. Figures 4A to 4E It corresponds to Figure 3 The diagram shows a cross-sectional view along line A-A' and illustrates a method for manufacturing a semiconductor device according to an example embodiment.

[0071] refer to Figure 1 and Figure 2 A method for manufacturing a semiconductor device according to embodiments of the present disclosure may include: forming a first resist layer on a substrate (S10), forming a second resist layer on the first resist layer (S20), exposing a first region of the second resist layer (S30), forming a photoresist pattern by performing a heat treatment on the second resist layer to remove an unexposed second region of the second resist layer (S40), and processing the first resist layer using the photoresist pattern (S50). The formation of the photoresist pattern (S40) may include performing a first heat treatment on the second resist layer to crosslink the first region (S41), and performing a second heat treatment on the second resist layer to remove the second region (S42). This will be described in detail with reference to the accompanying drawings.

[0072] refer to Figure 1 , Figure 3 and Figure 4AA substrate 100 can be fabricated. The substrate 100 can be the etching target of the photoresist pattern 300P. For example, the substrate 100 can be a material processed in an etching process to obtain the desired pattern shape by a photolithography process. The substrate 100 can include elemental semiconductor materials such as silicon (Si) or germanium (Ge), or compound semiconductor materials such as SiGe, SiC, GaAs, InAs, or InP. However, the substrate 100 is not limited to these and can be formed from various materials such as metals, glass, or polymer resins.

[0073] In the example embodiment, a thin film may be formed on substrate 100. The etching target may be the thin film rather than substrate 100. The thin film may be an insulating layer, a conductive layer, or a semiconductor layer. The thin film may be formed from, for example, metals, alloys, metal carbides, metal nitrides, metal oxide nitrides, metal carbon oxides, semiconductors, polysilicon, oxides, nitrides, oxide nitrides, or combinations thereof, but the example embodiment is not limited thereto. In the example embodiment, the coating process of the thin film may be omitted.

[0074] In an example embodiment, a bottom antireflective coating (BARC) may be selectively formed on substrate 100. The BARC layer can control the scattering of light from a light source used during an exposure process for manufacturing a semiconductor device, or absorb light reflected from substrate 100. The BARC layer may be formed from an organic antireflective coating (ARC) material for KrF excimer lasers, ArF excimer lasers, or any other light source. In an example embodiment, the BARC layer may include an organic component having a light-absorbing structure. The light-absorbing structure may be, for example, a hydrocarbon compound having one or more benzene rings or a structure in which benzene rings are fused. In an example embodiment, the BARC layer may be formed to a thickness of approximately 5 nm to approximately 100 nm, but the example embodiment is not limited thereto. In an example embodiment, the formation of the BARC layer may be omitted.

[0075] Then, the formation of a first resist layer on the substrate S10 can be performed. For example, the first resist layer 200 can be formed on the substrate 100 by drying and heat treatment. The heat treatment can be performed at a temperature of about 100°C to about 300°C. The first resist layer 200 can be used as an adhesive layer to bond the subsequently formed second resist layer 300 to the substrate 100. The first resist layer 200 may include, for example, a polymer resin. Furthermore, the first resist layer 200 may include at least a portion of the additives included in the photoresist composition described above. In the example embodiment, the formation of the first resist layer 200 may be omitted.

[0076] Next, a second resist layer can be formed on the first resist layer (S20). The second resist layer 300 can be formed by coating the photoresist composition described above onto the first resist layer 200. The second resist layer 300 can be in a cured form obtained by coating the photoresist composition and then performing a heat treatment process.

[0077] For example, forming a second resist layer on the first resist layer 200 may include applying a photoresist composition to the first resist layer 200 by spin coating, spraying, dip coating, aerosol coating, inkjet printing, etc., and may include drying the applied photoresist composition to form the second resist layer 300.

[0078] Next, a pre-exposure baking (PEB) process can be performed. The PEB process can be a process of heating the substrate 100 on which the first resist layer 200 and the second resist layer 300 are formed. The solvent in the second resist layer 300 can be removed by the PEB process.

[0079] refer to Figure 1 , Figure 2 and Figure 4B The first region of the second resist layer can be exposed (S30). For example, an exposure process can be performed to align the photomask 400 on the second resist layer 300, and light can be irradiated onto the second resist layer 300 through the photomask 400.

[0080] The light can be in the ultraviolet wavelength range, for example, between approximately 13.5 nm and 248 nm. The light in the ultraviolet wavelength range can be, for example, selected from a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), or an F2 excimer laser (157 nm). In an example embodiment, the light can be in the extreme ultraviolet (EUV) wavelength range (13.5 nm).

[0081] The photomask 400 may include a transparent substrate 430 and a plurality of light-shielding patterns 410 formed in a plurality of light-shielding regions on the transparent substrate 430. The transparent substrate 430 may be formed of quartz. The plurality of light-shielding patterns 410 may be formed of chromium (Cr), but the example embodiment is not limited thereto. A plurality of light-transmitting regions R1 and light-shielding regions R2 may be defined by the plurality of light-shielding patterns 410. The light-transmitting region R1 is the region in which no light-shielding pattern 410 is formed, while the light-shielding region R2 is the region in which a light-shielding pattern 410 is formed.

[0082] The second resist layer 300 may include a first region 310 and a second region 330. The region within the second resist layer 300 exposed to light is the first region 310, and the region not exposed to light (e.g., the region other than the first region 310) is the second region 330. As the exposure process is performed, the bonds between the central metal atom and the organic functional group of the organometallic compound present in the first region 310 may break. For example, in the organometallic compound present in the first region 310, at least a portion of the bonds between the central metal atom and two or more alkyl, aryl, or cycloalkyl groups covalently bonded to the central metal atom may break. The bonds between the central metal atom and one or more halogen groups covalently bonded to the central metal atom may remain intact without breaking.

[0083] For example, when the organometallic compound includes a compound represented by Formula 1, tin (Sn), as the central metal atom of the compound represented by Formula 1 present in the first region 310, and R 1 and / or R 2 The bonds between them can break.

[0084] refer to Figure 1 , Figure 2 and Figure 4C The process can involve heat-treating the second resist layer to remove unexposed second regions of the second resist layer to form a photoresist pattern (S40). For example, a first heat treatment process can be performed. The first heat treatment process can be an operation that heat-treats the second resist layer to crosslink the first region (S41). The first heat treatment allows the central metal atoms of the organometallic compound in the first region 310 to react with other organometallic compounds. For example, a first heat treatment process can be performed that allows crosslinking reactions to occur between organometallic compounds. Therefore, the first region 310 can be polymerized through the crosslinking reaction. As a result, the boiling point of the organometallic compound in the first region 310 can be increased.

[0085] Next, a second heat treatment process can be performed. This second heat treatment can be an operation to remove the second region by performing a second heat treatment on the second resist layer (S42). For example, the second heat treatment process can be performed by immediately increasing the temperature after the first heat treatment, and the photoresist composition in the second region 330 can be vaporized by the second heat treatment. Therefore, the second region 330 of the second resist layer 300 can be removed. As a result, a photoresist pattern 300P can be formed.

[0086] In the example embodiment, the boiling point of the organometallic compound may be higher than the temperature at which the first heat treatment is performed and lower than the temperature at which the second heat treatment is performed. The boiling point of the organometallic compound in the first region 310, where the crosslinking reaction has occurred, may be higher than the temperature at which the second heat treatment is performed. For example, the boiling point of the organometallic compound may be from about 200°C to about 250°C, or any range thereof. The first heat treatment may be performed at a temperature, for example, from about 110°C to about 180°C, or any range thereof. The second heat treatment may be performed at a temperature, for example, from about 200°C to about 280°C, or any range thereof.

[0087] In an example embodiment, the boiling point of the organometallic compound is higher than the temperature at which the first heat treatment is performed, such that the organometallic compound in the second region 330 may not be vaporized during the first heat treatment, and the crosslinking reaction may occur in the exposed first region 310. In some embodiments, the boiling point of the organometallic compound is lower than the temperature at which the second heat treatment is performed, such that the organometallic compound in the second region 330 with a relatively low boiling point and not undergoing a crosslinking reaction may be vaporized during the second heat treatment. Based on this principle, a photoresist pattern can be formed without a development process. As a result, the process can be simplified, and defects caused by the collapse of the photoresist pattern and photoresist pattern residues that occur during the development process can be prevented.

[0088] Back Figure 3 The photoresist pattern 300P can have multiple holes in a top view. Each hole can be circular. The holes of the photoresist pattern 300P can be arranged in a honeycomb pattern, but the shape of the holes is not limited to this. For example, the shape of the holes of the photoresist pattern 300P can be changed to various shapes such as serrated, polygonal, or circular. In addition, the planar shape of the photoresist pattern 300P can be changed differently. The photoresist pattern 300P can have, for example, a linear planar shape including a portion extending in one direction.

[0089] The photoresist pattern 300P formed by the process described above will not experience pattern collapse even when forming patterns with high aspect ratios. Therefore, the photoresist pattern 300P can have a width of 5 nm to 100 nm, or any range thereof. The photoresist pattern 300P can be formed with a width of, for example, 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, or 5 nm to 20 nm.

[0090] refer to Figure 1 and Figure 4DThe process of processing the first resist layer using a photoresist pattern (S50) can be performed. An etching process can be performed to selectively etch the first resist layer 200. For example, a photoresist pattern 300P can be used as an etching mask to selectively etch the first resist layer 200 in areas not covered by the photoresist pattern 300P. Thus, a lower pattern 200P can be formed. The lower pattern 200P can have a width corresponding to the width of the photoresist pattern 300P.

[0091] refer to Figure 4E An etching process can be performed to etch the target. The photoresist pattern 300P can be used as an etching mask to perform the etching process. For example, the substrate 100 can be etched using the photoresist pattern 300P as an etching mask through a dry or wet etching process. Therefore, after etching the substrate 100, the photoresist pattern 300P and the underlying pattern 200P can be removed by an additional etching process.

[0092] Semiconductor devices can be ultimately manufactured using manufacturing methods that include the operations described above.

[0093] In the example embodiment, unlike the description above, the process of forming the first resist layer can be omitted. Additionally, various processes can be performed, such as etching a thin film formed on the substrate using a photoresist pattern, implanting impurity ions into a portion of the substrate, forming an additional layer on the substrate through an opening, or modifying a portion of the substrate through an opening. The photoresist pattern formed based on the operations described above can be used, for example, to form vertical channel transistors for DRAM.

[0094] As described above, according to the example embodiments, a method for manufacturing semiconductor devices with simplified processes and increased productivity can be provided.

[0095] While exemplary embodiments have been shown and described above, those skilled in the art will understand that modifications and variations can be made without departing from the scope of the inventive concept as defined in the appended claims.

Claims

1. A method for manufacturing a semiconductor device, the method comprising: A first resist layer is formed on the substrate; A second anti-corrosion layer is formed on the first anti-corrosion layer; The first area of ​​the second anti-corrosion layer is exposed; A photoresist pattern is formed by performing a heat treatment on the second resist layer to remove the unexposed second area of ​​the second resist layer; and The first resist layer is processed using the photoresist pattern.

2. The method according to claim 1, wherein, The formation of the photoresist pattern includes: Perform a first heat treatment on the second resist layer to crosslink the first region; and A second heat treatment is performed on the second resist layer to remove the second region.

3. The method according to claim 2, wherein, The first heat treatment is performed at a lower temperature than the second heat treatment.

4. The method according to claim 2, wherein, The second resist layer comprises an organometallic compound, additives, and a solvent, and The boiling point of the organometallic compound is higher than the temperature at which the first heat treatment is performed and lower than the temperature at which the second heat treatment is performed.

5. The method according to claim 4, wherein, The organometallic compounds include: Metal, wherein the metal is the central atom; Two or more hydrocarbon groups, said two or more hydrocarbon groups being covalently bonded to said metal; and One or more fluorine (F), chlorine (Cl), bromine (Br), or iodine (I) molecules, each covalently bonded to the metal. The metal is selected from polonium (Po), tellurium (Te), titanium (Ti), lead (Pb), gold (Au), silver (Ag), cesium (Cs), bismuth (Bi), tin (Sn), hafnium (Hf), zinc (Zn), cobalt (Co), aluminum (Al), antimony (Sb), indium (In), cadmium (Cd), or astatine (At), and Each of the hydrocarbon groups is independently a substituted or unsubstituted C1 to C12 alkyl, a substituted or unsubstituted C5 to C8 cycloalkyl, or a substituted or unsubstituted C6 to C14 aryl.

6. The method according to claim 5, wherein, The metal in question is tetravalent tin (Sn).

7. The method according to claim 5, wherein, The organometallic compounds include those represented by the following chemical formula 1: [Chemical Formula 1] Among them, R 1 and R 2 Each is independently a substituted or unsubstituted C1 to C12 alkyl, a substituted or unsubstituted C5 to C8 cycloalkyl, or a substituted or unsubstituted C6 to C14 aryl, and X 1 and X 2 Each is independently one of fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

8. The method according to claim 5, wherein, The organometallic compound includes at least one compound selected from the following: 。 9. The method according to claim 5, wherein, The organometallic compounds include those represented by the following chemical formula 2: [Chemical Formula 2] Among them, R 3 R 4 and R 5 Each is independently a substituted or unsubstituted C1 to C12 alkyl, a substituted or unsubstituted C5 to C8 cycloalkyl, or a substituted or unsubstituted C6 to C14 aryl, and X 3 It is fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

10. The method according to claim 4, wherein, The solvent includes at least one selected from ethers, alcohols, glycol ethers, aromatic hydrocarbons, ketones, and esters.

11. The method according to claim 4, wherein, The additive includes at least one selected from crosslinking agents, surfactants, dispersants, hygroscopic agents, or coupling agents.

12. The method according to claim 1, wherein, The exposure of the first region of the second resist layer is performed by extreme ultraviolet light.

13. The method according to claim 1, wherein, The second resist layer is non-chemically amplified.

14. A method for manufacturing a semiconductor device, the method comprising: A first resist layer is formed on the substrate; A second anti-corrosion layer is formed on the first anti-corrosion layer; The first area of ​​the second anti-corrosion layer is exposed; The second resist layer is subjected to heat treatment to form a photoresist pattern; and The underlying layer is processed using the aforementioned photoresist pattern. in, The formation of the photoresist pattern includes: A first heat treatment is performed at a temperature of 110°C to 180°C to crosslink the first region and the first resist layer; and A second heat treatment is performed at a temperature of 200°C to 280°C to remove the unexposed second area of ​​the second resist layer. The second resist layer comprises an organometallic compound, additives, and a solvent. The organometallic compounds include: Metal; Two or more hydrocarbon groups, said two or more hydrocarbon groups being covalently bonded to said metal; and One or more fluorine (F), chlorine (Cl), bromine (Br), or iodine (I) molecules, each covalently bonded to the metal. The metal is polonium (Po), tellurium (Te), titanium (Ti), lead (Pb), gold (Au), silver (Ag), cesium (Cs), bismuth (Bi), tin (Sn), hafnium (Hf), zinc (Zn), cobalt (Co), aluminum (Al), antimony (Sb), indium (In), cadmium (Cd), or astatine (At). Each of the hydrocarbon groups is independently a substituted or unsubstituted C1 to C12 alkyl, a substituted or unsubstituted C5 to C8 cycloalkyl, or a substituted or unsubstituted C6 to C14 aryl, and The boiling point of the organometallic compound is higher than the temperature at which the first heat treatment is performed and lower than the temperature at which the second heat treatment is performed.

15. The method according to claim 14, wherein, The metal in question is tetravalent tin (Sn).

16. The method of claim 14, wherein, The organometallic compound is a mixture of compounds represented by the following chemical formulas 1 and 2: [Chemical Formula 1] [Chemical Formula 2] Among them, R 1 To R 5 Each is independently a substituted or unsubstituted C1 to C12 alkyl, a substituted or unsubstituted C5 to C8 cycloalkyl, or a substituted or unsubstituted C6 to C14 aryl, and X 1 To X 3 Each is independently one of fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

17. A photoresist composition, said photoresist composition comprising: Organometallic compounds, additives, and solvents in, The organometallic compounds include: Tetravalent tin (Sn), with tetravalent tin (Sn) as the central metal atom; Two or more hydrocarbon groups, said two or more hydrocarbon groups covalently bonded to said tin; and One or more fluorine (F), chlorine (Cl), bromine (Br), or iodine (I) atoms, each covalently bonded to the tin, and Each of the hydrocarbon groups is independently a substituted or unsubstituted C1 to C12 alkyl, a substituted or unsubstituted C5 to C8 cycloalkyl, or a substituted or unsubstituted C6 to C14 aryl.

18. The photoresist composition according to claim 17, wherein, The organometallic compounds include those represented by the following chemical formula 1: [Chemical Formula 1] Among them, R 1 and R 2 Each is independently a substituted or unsubstituted C1 to C12 alkyl, a substituted or unsubstituted C5 to C8 cycloalkyl, or a substituted or unsubstituted C6 to C14 aryl, and X 1 and X 2 Each can be independently fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

19. The photoresist composition according to claim 17, wherein, The organometallic compound includes at least one compound selected from the following: 。 20. The photoresist composition according to claim 17, wherein, The organometallic compounds include those represented by the following chemical formula 2: [Chemical Formula 2] Among them, R 3 R 4 and R 5 Each is independently a substituted or unsubstituted C1 to C12 alkyl, a substituted or unsubstituted C5 to C8 cycloalkyl, or a substituted or unsubstituted C6 to C14 aryl, and X 3 It is one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).

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