Edge bead removal composition, developer composition, and method of forming pattern

Abstract

Provided are a composition selected from the group consisting of a composition for removing edge beads from a metal-containing resist and a developer composition for a metal-containing resist, and a method of forming a pattern using the same, the composition comprising: a compound comprising at least two ketone groups; and an organic solvent comprising at least one selected from the group consisting of acetate-based solvents and alcohol-based solvents wherein a compound comprising at least two ketone groups is included in an amount of about 10 wt% to about 70 wt%, based on the total weight of the composition, and the organic solvent is included in an amount of about 30 wt% to about 90 wt%, based on the total weight of the composition.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2023-0136003 filed in the Korean Intellectual Property Office on October 12, 2023, the entire contents of which are hereby incorporated herein by reference. Technical Field

[0003] Embodiments of the present disclosure relate to compositions for removing edge beads from metal-containing resists and / or developer compositions for metal-containing resists, and methods of forming patterns using the compositions. Background Art

[0004] In recent years, the semiconductor industry has been accompanied by a substantial continuous reduction in critical dimensions, and this reduction in dimensions has been facilitated by new types (or new classes) of high-performance photoresist materials and patterning methods that meet the interest in processing and patterning with increasingly smaller features.

[0005] With the recent rapid development of the semiconductor industry, semiconductor devices have improved operating speeds and large storage capacities, and based on such improvements, process technologies for improving the integration, reliability, and response speed of semiconductor devices are being developed. It is important to accurately control / implant impurities in working regions of a silicon substrate and interconnect these regions to form devices and ultra-high density integrated circuits, which can be achieved through a photolithographic process. It is important to integrate a photolithographic process including coating a photoresist on a substrate, selectively exposing the photoresist to ultraviolet (UV) (including extreme ultraviolet (EUV)), electron beams, X-rays, and / or the like, and then developing the photoresist.

[0006] In the process of forming a photoresist layer, the resist can be applied to the substrate while the silicon substrate is rotated, wherein the resist is applied to the edge and rear surface of the substrate, which may cause pattern defects in subsequent semiconductor processes (such as etching processes and ion implantation processes). Therefore, a process of stripping and removing the photoresist applied to the edge and rear surface of the silicon substrate by using a thinner composition is implemented, such as an edge bead removal (EBR) process. The EBR process utilizes the following composition, which exhibits excellent solubility to the photoresist and effectively removes the beads and photoresist retained in the substrate without or substantially without generating resist residues.

[0007] There is interest in developing a photoresist capable of ensuring excellent etch resistance and resolution in a photolithography process while improving sensitivity and critical dimension (CD) uniformity and capable of improving line edge roughness (LER) characteristics, and a developer composition capable of implementing the same. Summary of the invention

[0008] Some embodiments of the present disclosure provide a composition for removing edge beads from a metal-containing resist and / or a developer composition for a metal-containing resist.

[0009] Some embodiments provide a method of forming a pattern using the composition.

[0010] A composition for removing edge beads from a metal-containing resist and / or a developer composition for a metal-containing resist according to some embodiments includes: a compound including at least two ketone groups; and an organic solvent including at least one selected from an acetate-based solvent and an alcohol-based solvent,

[0011] The compound comprising at least two keto groups is included in an amount of about 10 wt % to about 70 wt % based on the total weight of the composition, and the organic solvent is included in an amount of about 30 wt % to about 90 wt % based on the total weight of the composition.

[0012] The method of forming a pattern according to some embodiments includes: coating a metal-containing resist composition on a substrate; coating a composition for removing edge beads from the metal-containing resist along an edge of the substrate to remove the metal-containing resist edge beads; performing drying and heating to form a metal-containing photoresist film on the substrate; exposing the metal-containing photoresist film; and performing development using a developer composition for the metal-containing resist.

[0013] Wherein at least one selected from a composition for removing edge beads from a metal-containing resist and a developer composition for a metal-containing resist comprises the aforementioned composition.

[0014] Compositions for removing edge beads from metal-containing resists according to some embodiments reduce metal-based contamination inherent in metal-containing resists and remove resist coated on the edge and back surface of a substrate, thereby meeting the demand for processing and patterning of smaller features.

[0015] The developer composition of the metal-containing resist according to some embodiments provides excellent contrast characteristics, excellent sensitivity, and reduced line edge roughness (LER) by minimizing defects present in the metal-containing photoresist film after an exposure process and facilitating development. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The drawings, together with the specification, illustrate embodiments of the presently disclosed subject matter, and, together with the description, serve to explain principles of the embodiments of the presently disclosed subject matter.

[0017] Figure 1 is a schematic diagram of a photoresist coating apparatus.

[0018] Figures 2 to 4 are cross-sectional views illustrating a process sequence according to an embodiment of a method of forming a pattern.

[0019] [Explanation of Reference Numerals]

[0020] 1: substrate support part;

[0021] 2: Nozzle;

[0022] 10: photoresist solution;

[0023] 12: edge beads;

[0024] 100: substrate;

[0025] 110: feature layer;

[0026] 110P: characteristic pattern;

[0027] 130P: photoresist pattern;

[0028] OP: Opening;

[0029] W: substrate. DETAILED DESCRIPTION

[0030] Hereinafter, embodiments of the present disclosure are described in more detail with reference to the accompanying drawings. In the following description of the present disclosure, well-known functions or configurations may not be described in detail for the sake of clarity.

[0031] In order to clearly illustrate the embodiments of the present disclosure, some descriptions and relationships may be omitted, and the same or similar configuration elements are represented by the same reference numerals throughout the disclosure. In addition, since the size and thickness of each configuration shown in the drawings may be arbitrarily shown for better understanding and ease of description, the present disclosure is not necessarily limited thereto.

[0032] In the drawings, the thickness of each layer, film, panel, region, etc. may be exaggerated for clarity. In the drawings, the thickness of a portion of each layer or region may be exaggerated for clarity. It should be understood that when an element (such as a layer, film, region, or substrate) is referred to as being "on" another element, the element may be directly on the other element or intervening elements may also be present.

[0033] In the present disclosure, the term "substituted" means that a hydrogen atom is replaced by a deuterium, a halogen, a hydroxyl group, a thiol group, a cyano group, a carbonyl group, an amino group, a substituted or unsubstituted C1 to C30 amino group, a nitro group, a substituted or unsubstituted C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 haloalkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, or a C1 to C20 sulfide group. The term "unsubstituted" means that a hydrogen atom remains as a hydrogen atom without being replaced by another substituent.

[0034] In the present disclosure, unless otherwise defined, the term "alkyl" means a straight or branched aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" not including any double bond or triple bond.

[0035] The alkyl group may be a C1 to C20 alkyl group. In some embodiments, the alkyl group may be a C1 to C10 alkyl group or a C1 to C6 alkyl group. For example, the C1 to C5 alkyl group may have an alkyl chain containing 1 to 5 carbon atoms and may be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

[0036] Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl and the like.

[0037] In the chemical formulas described herein, t-Bu refers to a tert-butyl group.

[0038] In the present disclosure, when a definition is not otherwise provided, the term "cycloalkyl group" refers to a monovalent cyclic aliphatic hydrocarbon group.

[0039] Cycloalkyl groups may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

[0040] The cycloalkyl group may be a C3 to C10 cycloalkyl group, such as a C3 to C8 cycloalkyl group, a C3 to C7 cycloalkyl group, or a C3 to C6 cycloalkyl group. For example, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, but is not limited thereto.

[0041] In the present disclosure, when a definition is not otherwise provided, the "alkenyl group" may be a linear or branched aliphatic hydrocarbon group, and may refer to an aliphatic unsaturated alkenyl group containing one or more double bonds.

[0042] In the present disclosure, when a definition is not otherwise provided, the "alkynyl group" may be a linear or branched aliphatic hydrocarbon group, and may refer to an unsaturated alkynyl group containing one or more triple bonds.

[0043] In the present disclosure, the term "aryl group" means a substituent in which all elements of a cyclic substituent have p-orbitals, and these p-orbitals form a conjugated portion, and may include a monocyclic functional group, a polycyclic functional group, or a condensed ring (e.g., a ring sharing adjacent pairs of carbon atoms) functional group.

[0044] In an embodiment, the substituted or unsubstituted C6 to C30 aryl group may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted tetraphenyl group, a substituted or unsubstituted pyrene group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted o-terphenyl group, a substituted or unsubstituted chrysene group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, or a combination thereof, but is not limited thereto.

[0045] Figure 1 is a schematic diagram showing a photoresist coating apparatus.

[0046] Reference Figure 1 The photoresist coating apparatus is equipped with a substrate supporting part 1 on which a substrate W is placed, and the substrate supporting part 1 includes a spin chuck or a spin coater.

[0047] The substrate support part 1 rotates in a first direction at a set or predetermined rotation speed to provide centrifugal force to the substrate W. A nozzle 2 may be positioned on or above the substrate support part 1, but the position of the nozzle 2 is away from the upper part of the substrate W in the standby area, so that the nozzle can move toward the upper part of the substrate W in the spraying step and spray the photoresist solution 10. For example, the nozzle 2 may be located above the substrate support part 1 and spaced apart from the substrate support part 1, and the nozzle 2 may move toward or away from the substrate support part 1. Therefore, the photoresist solution 10 is coated on the surface of the substrate W by the centrifugal force. Herein, the photoresist solution 10 supplied to the center of the substrate W is coated while being diffused to the edge of the substrate W by the centrifugal force, wherein a portion of the photoresist solution 10 moves to the side surface of the substrate W and the lower surface of the edge of the substrate.

[0048] In an embodiment, in the coating process, the photoresist solution 10 is mainly coated by a spin coating method, wherein a set or predetermined amount of photoresist solution 10 having a viscosity (e.g., a set viscosity) is supplied to the central portion of the substrate W and gradually diffuses toward the edge of the substrate W by centrifugal force.

[0049] Therefore, the photoresist film is uniformly formed by the rotation speed of the substrate supporting portion.

[0050] Such rotation evaporates the solvent from the photoresist solution 10 and thereby gradually increases the viscosity of the photoresist solution 10, thereby causing a relatively large amount of photoresist solution 10 to accumulate on the edge of the substrate due to the effect of surface tension, and even severely accumulate on the lower surface of the edge of the substrate. These accumulations of photoresist solution 10 are called edge beads 12.

[0051] Hereinafter, a composition for removing edge beads from a metal-containing resist and / or a developer composition for a metal-containing resist according to some embodiments is described.

[0052] A composition for removing edge beads from a metal-containing resist and / or a developer composition for a metal-containing resist according to some embodiments includes: a compound including at least two ketone groups; and an organic solvent including at least one selected from an acetate-based solvent and an alcohol-based solvent.

[0053] The compound comprising at least two keto groups is included in an amount of about 10 wt % to about 70 wt % based on the total weight of the composition, and the organic solvent is included in an amount of about 30 wt % to about 90 wt % based on the total weight of the composition.

[0054] The compound including at least two keto groups can adjust the sensitivity so that the photoresist film exhibits a contrast ratio under a low exposure energy state, and thus can further increase the solubility difference between the exposed area and the unexposed area.

[0055] Therefore, the occurrence of scum and / or residual film in the unexposed area can be suppressed or reduced.

[0056] For example, the compound including at least two keto groups may be included in an amount of about 10 wt % to about 60 wt % based on the total weight of the composition.

[0057] For example, the compound including at least two keto groups may be included in an amount of about 10 wt % to about 50 wt % based on the total weight of the composition.

[0058] In some embodiments, the compound comprising at least two keto groups may comprise at least one halogen.

[0059] The compound including at least two keto groups may be represented by Chemical Formula 1 or Chemical Formula 2.

[0060] [Chemical formula 1]

[0061]

[0062] [Chemical formula 2]

[0063]

[0064] In Chemical Formula 1 and Chemical Formula 2,

[0065] R 1 To R 6 are each independently hydrogen, halogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof,

[0066] L 1 To L 4 are each independently a single bond (eg, a single covalent bond), a carbonyl group, a substituted or unsubstituted C1 to C20 alkylene group, or a combination thereof,

[0067] n1 to n5 are each independently an integer from 0 to 2,

[0068] n1+n2+n3 is 2 or greater than 2, and

[0069] n4+n5 is 1 or greater than 1.

[0070] In Chemical Formula 1, R 1 , R 2 , L 1 and L 2At least one of the may be halogen, C1 to C20 alkyl substituted by at least one halogen, C3 to C20 cycloalkyl substituted by at least one halogen, C2 to C20 alkenyl substituted by at least one halogen, C2 to C20 alkynyl substituted by at least one halogen, C6 to C30 aryl substituted by at least one halogen, C1 to C20 alkylene substituted by at least one halogen, or a combination thereof, and

[0071] In Chemical Formula 2, R 3 To R 6 , L 3 and L 4 At least one of them may be halogen, C1 to C20 alkyl substituted by at least one halogen, C3 to C20 cycloalkyl substituted by at least one halogen, C2 to C20 alkenyl substituted by at least one halogen, C2 to C20 alkynyl substituted by at least one halogen, C6 to C30 aryl substituted by at least one halogen, C1 to C20 alkylene substituted by at least one halogen, or a combination thereof.

[0072] In some embodiments, the compound comprising at least two keto groups may include at least one selected from a fluoro group and a chloro group. As used herein, "at least one selected from a fluoro group and a chloro group" may mean at least one selected from fluorine and chlorine (e.g., at least one selected from a fluorine atom and a chlorine atom).

[0073] In some embodiments, in Chemical Formula 1, R 1 , R 2 , L 1 and L 2At least one of the following may be fluoro; chloro; methyl substituted by at least one selected from fluoro and chloro; ethyl substituted by at least one selected from fluoro and chloro; propyl substituted by at least one selected from fluoro and chloro; butyl substituted by at least one selected from fluoro and chloro; isopropyl substituted by at least one selected from fluoro and chloro; tert-butyl substituted by at least one selected from fluoro and chloro; 2,2-dimethylpropyl substituted by at least one selected from fluoro and chloro; tert-pentyl substituted by at least one selected from fluoro and chloro; cyclopropyl substituted by at least one selected from fluoro and chloro; cyclobutyl substituted by at least one selected from fluoro and chloro; cyclopentyl substituted by at least one selected from fluoro and chloro; cyclohexyl substituted by at least one selected from fluoro and chloro ; vinyl substituted by at least one selected from fluoro and chloro; propenyl substituted by at least one selected from fluoro and chloro; butenyl substituted by at least one selected from fluoro and chloro; ethynyl substituted by at least one selected from fluoro and chloro; propynyl substituted by at least one selected from fluoro and chloro; butynyl substituted by at least one selected from fluoro and chloro; phenyl substituted by at least one selected from fluoro and chloro; tolyl substituted by at least one selected from fluoro and chloro; xylyl substituted by at least one selected from fluoro and chloro; methylene substituted by at least one selected from fluoro and chloro; ethylene substituted by at least one selected from fluoro and chloro; propylene substituted by at least one selected from fluoro and chloro, or a combination thereof, and in Chemical Formula 2, R 3 To R 6 , L 3 and L 4At least one of the substituted 1,2-dimethylpropyl group may be substituted by at least one selected from fluoro and chloro groups; methyl group substituted by at least one selected from fluoro and chloro groups; ethyl group substituted by at least one selected from fluoro and chloro groups; propyl group substituted by at least one selected from fluoro and chloro groups; butyl group substituted by at least one selected from fluoro and chloro groups; isopropyl group substituted by at least one selected from fluoro and chloro groups; tert-butyl group substituted by at least one selected from fluoro and chloro groups; 2,2-dimethylpropyl group substituted by at least one selected from fluoro and chloro groups; tert-amyl group substituted by at least one selected from fluoro and chloro groups; cyclopropyl group substituted by at least one selected from fluoro and chloro groups; cyclobutyl group substituted by at least one selected from fluoro and chloro groups; cyclopentyl group substituted by at least one selected from fluoro and chloro groups; substituted cyclohexyl; vinyl substituted with at least one selected from fluoro and chloro; propenyl substituted with at least one selected from fluoro and chloro; butenyl substituted with at least one selected from fluoro and chloro; ethynyl substituted with at least one selected from fluoro and chloro; propynyl substituted with at least one selected from fluoro and chloro; butynyl substituted with at least one selected from fluoro and chloro; phenyl substituted with at least one selected from fluoro and chloro; tolyl substituted with at least one selected from fluoro and chloro; xylyl substituted with at least one selected from fluoro and chloro; methylene substituted with at least one selected from fluoro and chloro; ethylene substituted with at least one selected from fluoro and chloro; propylene substituted with at least one selected from fluoro and chloro, or a combination thereof.

[0074] For example, a compound comprising at least two keto groups may comprise at least one fluoro group (eg, at least one fluorine atom).

[0075] For example, a compound comprising at least two keto groups can comprise at least one chloro group (eg, at least one chlorine atom).

[0076] The organic solvent included in the composition for removing edge beads from a metal-containing resist and / or the developer composition according to some embodiments may include at least one selected from acetate solvents and alcohol solvents, such as propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), propylene glycol butyl ether (PGBE), ethylene glycol methyl ether, diethylene glycol ethyl methyl ether, dipropyl glycol dimethyl ether, ethanol, 2-butoxyethanol, n-propanol, isopropanol, n-butanol, isobutanol, hexanol, ethylene glycol, propylene glycol, ethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diacetone alcohol, cyclohexanone, methyl-2-hydroxy-2-methylpropionate (HBM), gamma-butyrolactone (gamma- The invention also includes the following: butyrolactone, GBL), 1-butanol (n-butanol), ethyl lactate (EL), butyl lactate (n-butyl lactate), 4-methyl-2-pentenol (or methyl isobutyl carbinol, MIBC), 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutanoic acid, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, butyl acetate, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate or a mixture thereof, but is not limited thereto.

[0077] The composition for removing edge beads from a metal-containing resist according to the present disclosure can be particularly effective in removing metal-containing resists, and for example, undesirable metal residues, such as tin-based metal residues.

[0078] In embodiments, the developer composition of the metal-containing resist according to the present disclosure minimizes or reduces defects present in the metal-containing photoresist film after an exposure process and enables easy development, thereby achieving excellent pattern characteristics.

[0079] In embodiments, excellent sensitivity and reduced line edge roughness (LER) may be achieved.

[0080] The composition for removing edge beads from a metal-containing resist and / or the developer composition for the metal-containing resist may further include an acid compound, such as carboxylic acid, phosphoric acid, phosphorous acid, sulfuric acid, and / or the like.

[0081] In embodiments including other additives as further described below, an organic solvent may be included in the balance in addition to the included components.

[0082] The composition for removing edge beads from a metal-containing resist and / or the developer composition for a metal-containing resist may further include at least one other additive selected from a surfactant, a dispersant, a hygroscopic agent, and a coupling agent.

[0083] According to some exemplary embodiments, a method of forming a pattern includes removing edge beads using the aforementioned composition for removing edge beads from a metal-containing resist. For example, the pattern produced may be a photoresist pattern. In an embodiment, the photoresist pattern may be a negative photoresist pattern.

[0084] According to some embodiments, the method of forming a pattern includes: coating a metal-containing resist composition on a substrate; coating the aforementioned composition for removing edge beads from the metal-containing resist along the edge of the substrate; drying and heating to form a metal-containing photoresist film on the substrate; exposing the metal-containing photoresist film; and developing the metal-containing photoresist film.

[0085] For example, forming a pattern using a metal-containing resist composition may include: coating the metal-containing resist composition on a substrate having a thin film formed thereon by spin coating, slit coating, inkjet printing, etc., and drying the coated metal-containing resist composition to form a photoresist film. The metal-containing resist composition may include a tin compound, which may include, for example, at least one selected from a tin compound containing an organic oxygen group and a tin compound containing an organic carbonyl oxygen group.

[0086] In an embodiment, the composition for removing edge beads from the metal-containing resist may be applied along the edge of the substrate while the substrate is rotated at a suitable or appropriate speed (eg, 500 rpm or more).

[0087] Subsequently, a first heat treatment process of heating the substrate on which the photoresist film is formed is performed. The first heat treatment process may be performed at a temperature of about 80° C. to about 120° C., and in this process, the solvent is evaporated and the photoresist film may be more firmly bonded to the substrate.

[0088] Then, the photoresist film is selectively exposed.

[0089] Examples of light that can be used in the exposure process may include not only light with a short wavelength (e.g., i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm) and / or ArF excimer laser (wavelength 193nm)), but also light with a high energy wavelength (e.g., extreme ultraviolet (EUV) light, wavelength 13.5nm), electron beam (E-Beam), etc.

[0090] In an embodiment, the light used for exposure according to some exemplary embodiments may be short wavelength light having a wavelength range between about 5 nm and about 150 nm, and light having a high energy wavelength such as extreme ultraviolet light (EUV, wavelength 13.5 nm), electron beam (E-Beam), etc.

[0091] In forming the photoresist pattern, a negative type pattern may be formed.

[0092] The exposed region of the photoresist film has a solubility different from that of the unexposed region of the photoresist film because a polymer is formed by a cross-linking reaction (eg, a condensation reaction between organometallic compounds).

[0093] Then, a second heat treatment process is performed on the substrate. The second heat treatment process may be performed at a temperature of about 90° C. to about 200° C. By performing the second heat treatment process, the exposed area of ​​the photoresist film becomes difficult to dissolve in the developer.

[0094] For example, a photoresist pattern corresponding to a negative image may be completed by using an organic solvent (eg, 2-heptanone) to dissolve and remove the photoresist film corresponding to the unexposed area.

[0095] The developer used in the method of forming a pattern according to some embodiments may be an organic solvent, such as a ketone (e.g., methyl ethyl ketone, acetone, cyclohexanone and / or 2-heptanone), an alcohol (e.g., 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol and / or methanol), an ester (e.g., propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone), an aromatic compound (e.g., benzene, xylene and / or toluene), or a combination thereof.

[0096] As described above, the photoresist pattern formed by not only exposing to light having a short wavelength such as i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm) and / or ArF excimer laser (wavelength 193nm), but also exposing to light having high energy such as EUV (extreme ultraviolet light; wavelength 13.5nm) and electron beam (E-Beam) may have a thickness width of about 5nm to about 100nm. For example, the photoresist pattern may be formed to have a thickness width of about 5nm to about 90nm, about 5nm to about 80nm, about 5nm to about 70nm, about 5nm to about 60nm, about 5nm to about 50nm, about 5nm to about 40nm, about 5nm to about 30nm, or about 5nm to about 20nm.

[0097] In an embodiment, a half-pitch of a pitch of the photoresist pattern may be less than or equal to about 50 nm, for example, less than or equal to 40 nm, for example, less than or equal to 30 nm, for example, less than or equal to 20 nm, for example, less than or equal to 15 nm, and a line width roughness of the photoresist pattern may be less than or equal to about 10 nm, less than or equal to about 5 nm, less than or equal to about 3 nm, or less than or equal to about 2 nm.

[0098] According to some embodiments, a method of forming a pattern includes: coating a metal-containing resist composition on a substrate; removing edge beads of the metal-containing resist; drying and heating to form a metal-containing resist film on the substrate; exposing the metal-containing photoresist film; and developing using the aforementioned metal-containing resist developer composition.

[0099] The coating of the metal-containing resist composition on the substrate is the same as described above.

[0100] Removal of edge beads containing metal resist may be performed by applying a suitable or appropriate amount of any suitable organic solvent and / or composition for removing edge beads along the edge of the substrate while rotating the substrate at a suitable or appropriate speed (e.g., 500 rpm or greater).

[0101] Drying and heating are performed to form a metal-containing resist film on the substrate in the same manner as described above.

[0102] The exposure of the metal-containing photoresist film is performed in the same manner as described above.

[0103] By dissolving the photoresist film corresponding to the unexposed area using the aforementioned developer composition containing the metal resist and then removing the photoresist film, a photoresist pattern corresponding to the negative image can be completed.

[0104] The metal compound included in the metal-containing resist composition may include at least one selected from an organic oxygen group and an organic carbonyl oxygen group.

[0105] As an example, the metal compound included in the metal-containing resist composition may be represented by Chemical Formula 3.

[0106] [Chemical formula 3]

[0107]

[0108] In chemical formula 3,

[0109] R 7 is selected from substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and L a -OR a (Where L a is a substituted or unsubstituted C1 to C20 alkylene group, R a is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group),

[0110] R 8 To R 10 each independently represents halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, alkoxy or aryloxy (—OR b , where R b is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), a carboxyl group (—O(CO)R c , where R c is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof), an alkylamide or a dialkylamide (—NR d R e , where R d and R eare each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof), amido (-NR f (COR g ), where R f and R g are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof), or amidino (—NR h C(NR i )R j , where R h , R i and R j are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and

[0111] Selected from R 8 To R 10 At least one of them is independently halogen, alkoxy or aryloxy (-OR b , where R b is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), a carboxyl group (—O(CO)R c , where R c is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof), an alkylamide or a dialkylamide (—NR d R e , where R d and R eare each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof), amide (—NR f (COR g ), where R f and R g are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof), or amidino (—NR h C(NR i )R j , where R h , R i and R j each is independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof).

[0112] For example, the metal compound included in the metal-containing resist composition may include at least one selected from an alkoxy group and an alkylcarbonyloxy group.

[0113] Hereinafter, a method of forming a pattern by developing will be described in detail with reference to the accompanying drawings.

[0114] Figures 2 to 4 2 is a cross-sectional view showing a process sequence in order to explain a method of forming a pattern according to an embodiment of the present disclosure.

[0115] Reference Figure 2 , the exposed photoresist film on the substrate 100 is developed to form a photoresist pattern 130P.

[0116] In some embodiments, the exposed photoresist film may be developed to remove unexposed regions of the photoresist film, and a photoresist pattern 130P including the exposed regions of the photoresist film may be formed. The photoresist pattern 130P may include a plurality of openings OP.

[0117] In some embodiments, the development of the photoresist film may be performed by a negative-tone development (NTD) process. Herein, a metal-containing photoresist developer composition according to some embodiments may be used as a developer composition.

[0118] Reference Figure 3 , using photoresist pattern 130P for Figure 2 The resulting feature layer 110 is shown processed.

[0119] For example, the feature layer 110 is processed by the following various suitable processes: etching the feature layer 110 exposed by the opening OP of the photoresist pattern 130P; injecting impurity ions into the feature layer 110; forming an additional film on the feature layer 110 through the opening OP; deforming a portion of the feature layer 110 through the opening OP, etc. Figure 3 An exemplary process of processing the feature pattern 110P by etching the feature layer 110 exposed through the opening OP is shown.

[0120] Reference Figure 4 ,exist Figure 3 The resultant is shown with the photoresist pattern 130P remaining on the feature pattern 110P removed. To remove the photoresist pattern 130P, an ashing process and / or a stripping process may be used.

[0121] According to some embodiments, the method of forming a pattern includes: coating a metal-containing resist composition on a substrate; coating the aforementioned composition for removing edge beads from the metal-containing resist along the edge of the substrate; drying and heating to form a metal-containing photoresist film on the substrate; exposing the metal-containing photoresist film; and developing using the aforementioned developer composition of the metal-containing resist.

[0122] The method is specifically the same as described above, but in removing edge beads and developing, a composition for removing edge beads from a metal-containing resist and / or a developer composition for a metal-containing resist according to the present disclosure is used concurrently (e.g., simultaneously) to effectively improve the effect of removing edge beads and the solubility of unexposed areas, and thereby improve the processing and patterning of smaller features, thereby achieving excellent contrast characteristics, excellent sensitivity, and reduced line edge roughness (LER).

[0123] Hereinafter, the embodiments of the present disclosure will be described in more detail through examples related to the preparation of the aforementioned composition for removing edge beads from a metal-containing resist and a developer composition for a metal-containing resist. However, the technical features of the present disclosure are not limited to the following examples.

[0124] Preparation of a composition / developer composition for removing edge beads from a metal-containing resist

[0125] Examples 1 to 6 and Comparative Examples 1 to 5

[0126] One type of acetylacetone (AcAc), 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (1,1,1,5,5,5-hexafluoro-2,4-pentanedione (Hfac), 3-chloro-2,4-pentanedione (3-chloro-2,4-pentanedione, Cl-AcAc), formic acid (FA) and acetic acid (AA) were mixed with propylene glycol methyl ether acetate (PGMEA) as a solvent in each composition shown in Table 1, and then completely dissolved by shaking at room temperature (25° C.). Thereafter, the final composition was obtained by passing through a filter made of polytetrafluoroethylene (PTFE) having a pore size of 1 μm.

[0127] [Table 1]

[0128]

[0129] Preparation of photoresist composition containing organic metal

[0130] A photoresist composition was prepared by dissolving an organometallic compound containing a structural unit represented by Chemical Formula C in 4-methyl-2-pentanol at a concentration of 1 wt % and filtering the solution using a 0.1 μm polytetrafluoroethylene (PTFE) syringe filter.

[0131] [Chemical formula C]

[0132]

[0133] Evaluation 1: Evaluation of contrast performance and sensitivity

[0134] Each of the manufactured metal-containing photoresist (PR) compositions was spin-coated on an 8-inch wafer at 1,500 rpm for 30 seconds, and then heat-treated at 130° C. for 60 seconds to manufacture a coated wafer.

[0135] The coated wafer was exposed to light in a rectangular pattern of 1.2 cm×0.9 cm in size by using a KrF scanner (PAS 5500 / 700D, ASML) at a dose of 10 mJ to 100 mJ, heat-treated at 180° C. for 60 seconds, developed by applying the developer compositions according to Examples 1 to 6 and Comparative Examples 1 to 5, respectively, and finally heat-treated at 200° C. for 60 seconds, thereby completing the patterned wafer. The patterned wafer was measured with respect to the thickness of each exposure area to obtain a contrast curve, and the contrast performance (γ(contrast)) was calculated by the contrast curve, and the results are shown in Table 2.

[0136] γ(contrast)=1 / log(D 100 / D0)

[0137] D 100 =Exposure dose when PR starts to retain 100%

[0138] D0 = exposure dose when PR is completely removed

[0139] Evaluation 2: Evaluation of sensitivity and line edge roughness (LER)

[0140] A linear array of 50 circular pads with a diameter of 500 μm was projected onto the wafer using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). Here, the exposure time of the pads was adjusted so that an increasing EUV dose was applied to each pad.

[0141] Subsequently, the resist and the substrate obtained therefrom were exposed on a hot plate at 160° C. for 120 seconds, and then post-exposure baked (PEB). The baked films were immersed in the developer of the example and the comparative example for 30 seconds, respectively, and then a negative image was formed. Finally, the process was terminated by baking the film at 150° C. for 2 minutes on a hot plate. After measuring the sensitivity and LER from a field emission scanning electron microscope (FE-SEM) image, the sensitivity and line edge roughness were evaluated according to the following criteria, and the results are shown in Table 2.

[0142] Sensitivity evaluation criteria

[0143] -A: less than 16mJ / cm 2

[0144] -B: greater than or equal to 16mJ / cm 2

[0145] LER Evaluation Criteria

[0146] -○: less than or equal to 2nm

[0147] -△: greater than 2nm and less than or equal to 5nm

[0148] -X: greater than 5nm

[0149] [Table 2]

[0150] γ(contrast) Sensitivity LER Example 1 35 A ○ Example 2 31 A ○ Example 3 34 A ○ Example 4 31 A ○ Example 5 36 A ○ Example 6 32 A ○ Comparative Example 1 12 A X Comparative Example 2 24 B △ Comparative Example 3 20 B △ Comparative Example 4 38 A △ Comparative Example 5 26 B ○

[0151] * Half-pitch (HP): Half-pitch reference

[0152] Referring to Table 2, applying the metal-containing photoresist developer composition according to the Example provides excellent contrast performance and excellent sensitivity characteristics and achieves reduced line edge roughness, compared with applying the metal-containing photoresist developer composition according to the Comparative Example.

[0153] In the above, some embodiments of the present disclosure have been described and illustrated. However, it should be obvious to those skilled in the art that the present disclosure is not limited to the embodiments described herein, but can be modified and transformed in various appropriate ways without departing from the spirit and scope of the present disclosure. Therefore, the modified or transformed embodiments themselves should not be understood separately from the technical ideas and aspects of the present disclosure, and the modified embodiments are within the scope of the claims of the present disclosure and their equivalent forms.

Claims

1. A composition selected from a composition for removing edge beads from a metal-containing resist and a developer composition for a metal-containing resist, each of the composition for removing edge beads from a metal-containing resist and the developer composition for a metal-containing resist comprising: Compounds containing at least two keto groups; as well as An organic solvent comprising at least one selected from an acetate solvent and an alcohol solvent, The compound comprising at least two keto groups is included in an amount of 10 wt % to 70 wt % based on the total weight of the composition, and the organic solvent is included in an amount of 30 wt % to 90 wt % based on the total weight of the composition.

2. The composition according to claim 1, wherein: The compound including at least two keto groups is included in an amount of 10 wt % to 60 wt % based on the total weight of the composition.

3. The composition according to claim 1, wherein: The compound including at least two keto groups is included in an amount of 10 wt % to 50 wt % based on the total weight of the composition.

4. The composition according to claim 1, wherein: The compound comprising at least two keto groups comprises at least one halogen.

5. The composition according to claim 1, wherein: The compound containing at least two keto groups is represented by Chemical Formula 1 or Chemical Formula 2: [Chemical formula 1] [Chemical formula 2] In Chemical Formula 1 and Chemical Formula 2, R 1 To R 6 are each independently hydrogen, halogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, L 1 To L 4 are each independently a single bond, a carbonyl group, a substituted or unsubstituted C1 to C20 alkylene group, or a combination thereof, n1 to n5 are each independently an integer from 0 to 2, n1+n2+n3 is 2 or greater than 2, and n4+n5 is 1 or greater than 1.

6. The composition according to claim 5, wherein: In Chemical Formula 1, R 1 , R 2 , L 1 and L 2 At least one of is halogen, C1 to C20 alkyl substituted by at least one halogen, C3 to C20 cycloalkyl substituted by at least one halogen, C2 to C20 alkenyl substituted by at least one halogen, C2 to C20 alkynyl substituted by at least one halogen, C6 to C30 aryl substituted by at least one halogen, C1 to C20 alkylene substituted by at least one halogen, or a combination thereof, and In Chemical Formula 2, R 3 To R 6 , L 3 and L 4 At least one of them is halogen, C1 to C20 alkyl substituted by at least one halogen, C3 to C20 cycloalkyl substituted by at least one halogen, C2 to C20 alkenyl substituted by at least one halogen, C2 to C20 alkynyl substituted by at least one halogen, C6 to C30 aryl substituted by at least one halogen, C1 to C20 alkylene substituted by at least one halogen, or a combination thereof.

7. The composition according to claim 5, wherein: In Chemical Formula 1, R 1 , R 2 , L 1 and L 2 at least one of which is fluoro; chloro; methyl substituted by at least one selected from fluoro and chloro; ethyl substituted by at least one selected from fluoro and chloro; propyl substituted by at least one selected from fluoro and chloro; butyl substituted by at least one selected from fluoro and chloro; isopropyl substituted by at least one selected from fluoro and chloro; tert-butyl substituted by at least one selected from fluoro and chloro; 2,2-dimethylpropyl substituted by at least one selected from fluoro and chloro; tert-amyl substituted by at least one selected from fluoro and chloro; cyclopropyl substituted by at least one selected from fluoro and chloro; cyclobutyl substituted by at least one selected from fluoro and chloro; cyclopentyl substituted by at least one selected from fluoro and chloro cyclohexyl; vinyl substituted by at least one selected from fluoro and chloro; propenyl substituted by at least one selected from fluoro and chloro; butenyl substituted by at least one selected from fluoro and chloro; ethynyl substituted by at least one selected from fluoro and chloro; propynyl substituted by at least one selected from fluoro and chloro; butynyl substituted by at least one selected from fluoro and chloro; phenyl substituted by at least one selected from fluoro and chloro; tolyl substituted by at least one selected from fluoro and chloro; xylyl substituted by at least one selected from fluoro and chloro; methylene substituted by at least one selected from fluoro and chloro; ethylene substituted by at least one selected from fluoro and chloro; propylene substituted by at least one selected from fluoro and chloro, or a combination thereof, and In Chemical Formula 2, R 3 To R 6 , L 3 and L 4 at least one of which is fluoro; chloro; methyl substituted by at least one selected from fluoro and chloro; ethyl substituted by at least one selected from fluoro and chloro; propyl substituted by at least one selected from fluoro and chloro; butyl substituted by at least one selected from fluoro and chloro; isopropyl substituted by at least one selected from fluoro and chloro; tert-butyl substituted by at least one selected from fluoro and chloro; 2,2-dimethylpropyl substituted by at least one selected from fluoro and chloro; tert-amyl substituted by at least one selected from fluoro and chloro; cyclopropyl substituted by at least one selected from fluoro and chloro; cyclobutyl substituted by at least one selected from fluoro and chloro; cyclopentyl substituted by at least one selected from fluoro and chloro substituted cyclohexyl; vinyl substituted with at least one selected from fluoro and chloro; propenyl substituted with at least one selected from fluoro and chloro; butenyl substituted with at least one selected from fluoro and chloro; ethynyl substituted with at least one selected from fluoro and chloro; propynyl substituted with at least one selected from fluoro and chloro; butynyl substituted with at least one selected from fluoro and chloro; phenyl substituted with at least one selected from fluoro and chloro; tolyl substituted with at least one selected from fluoro and chloro; xylyl substituted with at least one selected from fluoro and chloro; methylene substituted with at least one selected from fluoro and chloro; ethylene substituted with at least one selected from fluoro and chloro; propylene substituted with at least one selected from fluoro and chloro, or a combination thereof.

8. The composition according to claim 1, wherein: The composition further includes the following acid compounds: carboxylic acid, phosphoric acid, phosphorous acid, sulfuric acid or a combination thereof.

9. A method for forming a pattern, comprising: coating a metal-containing resist composition on a substrate; applying a composition for removing edge beads from a metal-containing resist along an edge of the substrate to remove metal-containing resist edge beads; performing drying and heating to form a metal-containing photoresist film on the substrate; exposing the metal-containing photoresist film; as well as developing using a developer composition containing a metal resist, wherein at least one selected from the composition for removing edge beads from a metal-containing resist and the developer composition for a metal-containing resist is each the composition according to claim 1.

10. The method according to claim 9, wherein: The metal compound included in the metal-containing resist composition includes at least one selected from an organic oxygen group and an organic carbonyl oxygen group.

11. The method according to claim 9, wherein: The metal compound included in the metal-containing resist composition is represented by Chemical Formula 3: [Chemical formula 3] Among them, in chemical formula 3, R 7 is selected from substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and L a -OR a , where L a is a substituted or unsubstituted C1 to C20 alkylene group, and R a is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group, R 8 To R 10 each independently represents halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, -OR b 、-O(CO)R c 、-NR d R e 、-NR f (COR g ) or -NR h C(NR i )R j , Selected from R 8 To R 10 At least one of them is halogen, -OR b 、-O(CO)R c 、-NR d R e 、-NR f (COR g ) or -NR h C(NR i )R j , Where R b is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, wherein R c is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, wherein R d and R e are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, wherein R f and R g are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, wherein R h , R i and R j Each is independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof.

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