Composition for removing edge bead from metal-containing resist, developer composition, and method of forming pattern

Abstract

A composition for removing edge beads from a metal-containing resist, a developer composition of a metal-containing resist, and a method of forming a pattern using the same are disclosed. A composition according to one or more embodiments comprises: a C1 to C10 carboxylic acid compound substituted with at least one fluorine; and an organic solvent.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefits of Korean Patent Application No. 10-2023-0102399 filed in the Korean Intellectual Property Office on August 4, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure relates to a composition for removing edge beads from a metal-containing resist, a developer composition for the metal-containing resist, and a method of forming a pattern using the same. Background Art

[0004] In recent years, the semiconductor industry has witnessed a substantial continuous reduction in critical dimensions, and this reduction in dimensions has necessitated the development of new types (classes) of high performance photoresist (PR) materials and patterning methods that can meet the needs or desires for processing and patterning with increasingly smaller features.

[0005] In addition, with the recent rapid development of the semiconductor industry, it is expected or required that semiconductor devices have fast operating speeds and large storage capacities, and in accordance with such needs, process technologies for improving the integration, reliability, and response speed of semiconductor devices are being developed or pursued. For example, it is important or desirable to accurately control / implant impurities in a working region of a silicon substrate and interconnect these regions to form devices and / or ultra-high density integrated circuits. Ultra-high density integrated circuits can be achieved or realized by a photolithographic process. For example, it is important or desirable to integrate a photolithographic process including the following operations: coating a photoresist on a substrate, selectively exposing the photoresist to ultraviolet (UV) (including extreme ultraviolet (EUV)), an electron beam (E-Beam), X-rays, etc., and then developing the photoresist.

[0006] For example, in the process of forming a photoresist layer, while rotating the silicon substrate, the resist is mainly applied to the substrate (e.g., the top surface of the substrate), but the resist may also be applied to the edge and rear surface of the substrate, which may cause pattern defects in subsequent semiconductor processes (e.g., etching processes and / or ion implantation processes). Therefore, a process of stripping and removing the photoresist applied to the edge and rear surface of the silicon substrate using a thinner composition is implemented, i.e., an edge bead removal (EBR) process. The EBR process requires or needs a composition that exhibits excellent or suitable solubility for the photoresist and can effectively remove the beads and photoresist remaining in the substrate without generating resist residues.

[0007] Therefore, it is necessary or desirable to develop a photoresist that can improve sensitivity and critical dimension (CD) uniformity while ensuring excellent or appropriate etch resistance and resolution in a photolithography process and can improve line edge roughness (LER) characteristics, and a developer composition that can implement these necessary or desired features. Summary of the invention

[0008] Aspects according to one or more embodiments relate to a composition for removing edge beads from a metal-containing resist and / or a developer composition for a metal-containing resist.

[0009] An aspect according to one or more embodiments is directed to a method of forming a pattern using the composition.

[0010] Additional aspects will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the embodiments presented in the disclosure.

[0011] According to one or more embodiments, the composition according to one or more embodiments includes: a C1 to C10 carboxylic acid compound substituted with at least one fluorine; and an organic solvent. The composition is used to remove edge beads from a metal-containing photoresist and / or is a developer composition for a metal-containing photoresist.

[0012] According to one or more embodiments, the method for forming a pattern according to one or more embodiments includes: coating a metal-containing photoresist composition on a substrate, coating the aforementioned composition for removing edge beads from a metal-containing resist along an edge of the substrate, drying and heating to form a metal-containing photoresist layer on the substrate, exposing the metal-containing photoresist layer, and developing the metal-containing photoresist layer.

[0013] According to one or more embodiments, the method of forming a pattern according to one or more embodiments includes: coating a metal-containing photoresist composition on a substrate, removing edge beads of a metal-containing resist, drying and heating to form a metal-containing photoresist layer on the substrate, exposing the metal-containing photoresist layer, and developing the metal-containing photoresist layer using a developer composition of the aforementioned metal-containing resist.

[0014] According to one or more embodiments, the method for forming a pattern according to one or more embodiments includes: coating a metal-containing photoresist composition on a substrate; coating the aforementioned composition for removing edge beads from a metal-containing resist along the edge of the substrate, drying and heating to form a metal-containing photoresist layer on the substrate, exposing the metal-containing photoresist layer; and developing the metal-containing photoresist layer using the aforementioned developer composition of the metal-containing resist.

[0015] The composition for removing edge beads from metal-containing resist according to one or more embodiments reduces inherent metal-based contaminants in the metal-containing resist (e.g., reduces the inherent metal-based contaminants present), and removes the resist coated on the edge and rear surface of the substrate, thereby meeting the requirements for processing and patterning of smaller features.

[0016] The developer composition of the metal-containing resist according to one or more embodiments may implement excellent or appropriate contrast characteristics, excellent or appropriate sensitivity, and reduced line edge roughness (LER) by minimizing or reducing defects present in the metal-containing photoresist layer after an exposure process and facilitating development. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The above and other aspects, features and enhancements of certain embodiments of the present disclosure will become more apparent upon reading the following description in conjunction with the accompanying drawings, in which:

[0018] Figure 1 is a schematic diagram of a photoresist coating apparatus.

[0019] Figures 2 to 4 is a cross-sectional view schematically illustrating a process sequence of a method of forming a pattern according to one or more embodiments of the present disclosure.

[0020] Figure 5 is a contrast curve obtained by measuring the thickness of each exposure area on a patterned wafer.

[0021] [Explanation of Symbols]

[0022] 1: substrate support part;

[0023] 2: Nozzle;

[0024] 10: photoresist solution;

[0025] 12: edge beads;

[0026] 100: substrate;

[0027] 110: feature layer;

[0028] 110P: characteristic pattern;

[0029] 130P: photoresist pattern;

[0030] OP: Opening;

[0031] W: substrate. DETAILED DESCRIPTION

[0032] 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 constructions will not be described for clarity of the present disclosure.

[0033] In order to clearly illustrate the present disclosure, certain descriptions and relationships that should be understood by a person of ordinary skill in the art are not provided, and throughout the disclosure, the same or similar configuration elements are represented by the same reference numerals. In addition, since the size and thickness of each configuration shown in the drawings are arbitrarily shown for better understanding and ease of description, the present disclosure is not necessarily limited thereto.

[0034] In the drawings, the thickness of layers, films, panels, regions, etc. may be exaggerated for clarity. In the drawings, the thickness of a portion of layers, regions, etc. may be exaggerated for clarity. It should be understood that if an element such as a layer, film, region, or substrate is referred to as being "on" another element (for example, when an element such as a layer, film, region, or substrate is referred to as being "on" another element), it may be directly on the other element or intervening elements may also be present.

[0035] In the present disclosure, the term "substituted" means that a hydrogen atom is replaced by 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 thioether group. The term "unsubstituted" used herein means that a hydrogen atom remains as a hydrogen atom without being replaced by another substituent.

[0036] In the present disclosure, unless otherwise defined, the term "alkyl" refers to a straight or branched aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0037] The alkyl group may be a C1 to C20 alkyl group. For example, the alkyl group may be a C1 to C10 alkyl group or a C1 to C6 alkyl group. For example, "C1 to C5 alkyl group" means that the alkyl chain contains 1 to 5 carbon atoms and may be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

[0038] Non-limiting examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, and the like.

[0039] In the chemical formulas described herein, "t-Bu" means tert-butyl.

[0040] In the present disclosure, if a definition is not otherwise provided (eg, when a definition is not otherwise provided), the term "cycloalkyl group" refers to a monovalent cyclic aliphatic hydrocarbon group.

[0041] 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 the present disclosure is not limited thereto.

[0042] In the present disclosure, if a definition is not otherwise provided (eg, when a definition is not otherwise provided), the term "heterocycloalkyl group" refers to a cycloalkyl group including at least one heteroatom selected from N, O, S, P and Si.

[0043] In the present disclosure, if a definition is not otherwise provided (eg, when a definition is not otherwise provided), the term "alkenyl" refers to a straight or branched aliphatic hydrocarbon group, and may refer to an aliphatic unsaturated alkenyl group containing one or more double bonds.

[0044] In the present disclosure, if a definition is not otherwise provided (for example, when a definition is not otherwise provided), the term "alkynyl" refers to a straight or branched aliphatic hydrocarbon group, and may refer to an unsaturated alkynyl group containing one or more triple bonds.

[0045] In the present disclosure, the term "aryl" refers to a substituent in which all elements of the cyclic substituent have p-orbitals, and these p-orbitals form conjugation and may include monocyclic functional groups or polycyclic functional groups, fused ring (i.e., rings that share adjacent pairs of carbon atoms) functional groups.

[0046] As used herein, the term "heteroaryl" may refer to an aryl group comprising at least one heteroatom selected from N, O, S, P and Si. Two or more heteroaryl groups may be directly connected by a sigma bond, or if the heteroaryl group comprises two or more rings (e.g., when the heteroaryl group comprises two or more rings), the two or more rings may be fused. If the heteroaryl group is a fused ring (e.g., when the heteroaryl group is a fused ring), each ring may comprise one to three heteroatoms.

[0047] For example, 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 pyrenyl 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, and / or (e.g., any suitable) combination thereof, but the present disclosure is not limited thereto.

[0048] For example, the substituted or unsubstituted C2 to C30 heterocyclyl group may be a substituted or unsubstituted furanyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, or a substituted or unsubstituted quinolinyl group. , substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl or substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted benzonaphthofuranyl, substituted or unsubstituted benzonaphthothiophenyl, substituted or unsubstituted benzofuranofluorenyl, substituted or unsubstituted benzothiophenefluorenyl, and / or (e.g., any suitable) combination thereof, but the present disclosure is not limited thereto.

[0049] Figure 1 is a schematic diagram showing a photoresist coating apparatus.

[0050] Reference Figure 1, a substrate supporting part 1 on which a substrate W is placed is provided in the photoresist coating apparatus, and the substrate supporting part 1 includes a spin chuck or a spin coater.

[0051] 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. The nozzle 2 may be positioned above (or on) the substrate support part 1, but the position of the nozzle 2 in the atmospheric region is away from the upper portion of the substrate W (e.g., the nozzle 2 may be spaced apart from the upper surface of the substrate W), so that the nozzle may move toward the upper portion of the substrate W and spray the photoresist solution 10 in a spraying (e.g., action or task) step. Therefore, the photoresist solution 10 is applied on the surface of the substrate W by the centrifugal force. Herein, when the photoresist solution 10 supplied to the center of the substrate W is applied by diffusing to the edge of the substrate W by the centrifugal force, 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 W.

[0052] For example, in the coating process, the photoresist solution 10 is (e.g., mainly) coated by a spin coating method, in which a set amount or a predetermined amount of the photoresist solution 10 having a (e.g., suitable) viscosity is supplied to the central portion of the substrate W and gradually diffused toward the edge of the substrate W by centrifugal force.

[0053] Therefore, the photoresist is uniformly formed by the rotational movement (eg, speed) of the substrate supporting part.

[0054] Such rotation also evaporates solvent from the solution (e.g., photoresist solution 10) and thereby gradually increases its viscosity, thereby causing a portion of the photoresist (e.g., a relatively large amount of photoresist) to accumulate on the edge of the substrate due to surface tension, and some photoresist even accumulates on the lower surface of the edge of the substrate W, which is referred to as edge bead 12.

[0055] Hereinafter, a composition for removing edge beads from a metal-containing resist and / or a developer composition for a metal-containing resist according to one or more embodiments is described.

[0056] A composition for removing edge beads from a metal-containing resist (e.g., a metal-containing photoresist) and / or a developer composition for a metal-containing resist (e.g., a metal-containing photoresist) according to one or more embodiments includes: a C1 to C10 carboxylic acid compound substituted with at least one fluorine; and an organic solvent.

[0057] The C1 to C10 carboxylic acid compound substituted with at least one fluorine compound can promote the reaction with the photoresist in the exposed area, thereby further increasing the solubility difference between the exposed area and the unexposed area.

[0058] In addition, by including fluorine as an electron withdrawing group, an appropriate or suitable pKa for improving sensitivity and resolution can be maintained, which is very advantageous or desirable for achieving fine patterns and controlling scum.

[0059] In some embodiments, the C1 to C10 carboxylic acid compound substituted with at least one fluorine may be represented by Chemical Formula 1.

[0060] [Chemical formula 1]

[0061]

[0062] In Chemical Formula 1,

[0063] R 1 To R 3 may be each independently hydrogen, fluorine, a fluorine-containing group, or a substituted or unsubstituted C1 to C5 alkyl group,

[0064] n can be an integer from 1 to 5, and

[0065] R 1 To R 3 At least one of them may be fluorine or a fluorine-containing group.

[0066] For example, R 2 or R 3 At least one of them may be fluorine or a fluorine-containing group.

[0067] For example, R 2 and R 3 Each may independently be fluorine or a fluorine-containing group.

[0068] For example, R 2 and R 3 Each may independently be fluorine.

[0069] As an example, the C1 to C10 carboxylic acid compound substituted with at least one fluorine may be at least one of difluoroacetic acid, 2,2-difluoropropionic acid, trifluoroacetic acid, or monofluoroacetic acid.

[0070] In one or more embodiments, the composition for removing edge beads from a metal-containing resist and / or the developer composition for a metal-containing resist may include about 0.01 wt % to about 5 wt % of the aforementioned C1 to C10 carboxylic acid compound substituted with at least one fluorine, and about 95 wt % to about 99.99 wt % of an organic solvent.

[0071] In one or more embodiments, the composition for removing edge beads from a metal-containing resist and / or the developer composition of the metal-containing resist may include the aforementioned C1 to C10 carboxylic acid compound substituted with at least one fluorine in an amount of about 0.05 wt % to about 5 wt % (e.g., about 0.05 wt % to about 1 wt %, or about 0.05 wt % to about 0.5 wt %).

[0072] The organic solvent included in the composition for removing edge beads from a metal-containing resist and / or the developer composition according to one or more embodiments may include propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), propylene glycol butyl ether (PGMEA), propylene glycol methyl ether acetate ... 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, heptanone, propylene carbonate, butylene carbonate, diethyl ether, dibutyl ether, ethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diisoamyl ether, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, acetonitrile, diacetone alcohol, 3,3-dimethyl-2-butanone, N-methyl-2-pyrrolidone, dimethylacetamide, methyl-2-hydroxy-2-methylpropionate (HBM), gamma butyrolactone (GBL), 1-butanol, ethyl lactate (EL), diene butyl ether (DE ether (DBE), diisopropyl ether (DIAE), acetylacetone, 4-methyl-2-pentanol (or methylisobutyl carbinol (MIBC)), 1-methoxy-2-propanol, 1-ethoxy-2-propanol, toluene, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methylpropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, butyl acetate, butyl lactate, methyl 2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate, and / or (e.g., any suitable) mixtures (e.g., combinations) thereof, but the present disclosure is not limited thereto.

[0073] The composition for removing edge beads from a metal-containing resist (e.g., a metal-containing photoresist) according to one or more embodiments of the present disclosure can effectively (e.g., particularly effectively) remove the metal-containing resist, such as undesirable metal residues (e.g., tin-based metal residues).

[0074] In addition, the developer composition of the metal-containing resist (e.g., metal-containing photoresist) according to one or more embodiments of the present disclosure reduces or minimizes defects present in the metal-containing photoresist layer after the exposure process and enables easy development, thereby achieving excellent or suitable pattern characteristics.

[0075] Additionally, excellent or suitable sensitivity and reduced line edge roughness (LER) may be achieved.

[0076] In some embodiments, one or more other additives (to be described in more detail later) may be included, and an organic solvent may be included in a balance amount other than the other included components.

[0077] The one or more other additives may be selected from surfactants, dispersants, hygroscopic agents and coupling agents.

[0078] In one or more embodiments, the surfactant may be a sulfate salt, a sulfonate salt, a phosphate ester, a soap, an amine salt, a quaternary ammonium salt, polyethylene glycol, an alkylphenol ethylene oxide adduct, a polyol, a nitrogen-containing vinyl polymer, and / or a combination thereof (e.g., any suitable combination), but the present disclosure is not limited thereto. For example, the surfactant may include an alkylbenzene sulfonate salt, an alkylpyridinium salt, polyethylene glycol, or a quaternary ammonium salt.

[0079] In one or more embodiments, the dispersant may be epoxy resin, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, glucose, sodium lauryl sulfate, sodium citrate, oleic acid, linoleic acid, and / or (e.g., any suitable) combinations thereof, but the present disclosure is not limited thereto.

[0080] For example, the desiccant may be used to prevent or reduce oxidation of metal contained in the photoresist composition by moisture. In one or more embodiments, the desiccant may be polyoxyethylenenonylphenolether, polyethylene glycol, polypropylene glycol, polyacrylamide, and / or any suitable combination thereof, but the present disclosure is not limited thereto.

[0081] In one or more embodiments, the coupling agent may include a silane coupling agent. The silane coupling agent may be vinyl trimethoxysilane, vinyl triethoxysilane, vinyl trichlorosilane, vinyl tri(β-methoxyethoxy)silane, 3-methacryloxypropyl trimethoxysilane, 3-acryloxypropyl trimethoxysilane, p-phenylene trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane or trimethoxy [3- (phenylamino) propyl] silane, but the present disclosure is not limited thereto.

[0082] The metal compound included in the metal-containing resist (eg, metal-containing photoresist) may include at least one of an organic oxygen group-containing tin compound or an organic carbonyloxy group-containing tin compound.

[0083] As an example, the metal compound included in the metal-containing resist may be represented by Chemical Formula 2.

[0084] [Chemical formula 2]

[0085]

[0086] In chemical formula 2,

[0087] R 4 may be 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, substituted or unsubstituted C6 to C30 aralkyl, 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), and

[0088] R 5 To R 7 can be 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, and / or (e.g., any suitable) combination thereof), a carboxyl group (—O(CO)R 6 , where R 6is 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, and / or (e.g., any suitable) combination thereof), alkylamide or dialkylamide (—NR 7 R 8 , where R 7 and R 8 The alkyl groups may each independently be 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, and / or (e.g., any suitable) combination thereof), an amido group (-NR 9 (CO)R 10 , where R 9 and R 10 The substituted or unsubstituted C1-C20 alkyl group, the substituted or unsubstituted C3-C20 cycloalkyl group, the substituted or unsubstituted C2-C20 alkenyl group, the substituted or unsubstituted C2-C20 alkynyl group, the substituted or unsubstituted C6-C30 aryl group, and / or (e.g., any suitable) combination thereof), or an amidinato group (-NR 11 C(NR 12 )R 13 , where R 11 , R 12 and R 13 Each may independently be 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, and / or (e.g., any suitable) combination thereof).

[0089] For example, the metal compound included in the metal-containing resist may be at least one of an alkoxy-containing tin compound or an alkylcarbonyloxy-containing tin compound.

[0090] In one or more embodiments, the method of forming a pattern includes a step of 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, such as a negative or negative-type photoresist pattern.

[0091] The method of forming a pattern according to one or more embodiments 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 layer on the substrate, exposing the metal-containing photoresist layer, and developing the metal-containing photoresist layer.

[0092] 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, and / or the like, and drying the coated metal-containing resist composition to form a photoresist layer. The metal-containing resist composition may include a tin compound, and for example, the tin compound may include at least one of an organic oxygen group-containing tin compound or an organic carbonyl oxygen group-containing tin compound.

[0093] In an embodiment, the composition for removing edge beads from a metal-containing resist may be applied along the edge of the substrate while the substrate is rotated at an appropriate or suitable speed (eg, 500 rpm or more).

[0094] Subsequently, a first heat treatment process of heating the substrate on which the photoresist layer 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 layer may be more firmly bonded to the substrate.

[0095] Then, the photoresist layer is selectively exposed.

[0096] For example, examples of light that can be used in the exposure process may include not only light with a short wavelength (such as i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm), or ArF excimer laser (wavelength 193nm)) but also light with a high energy wavelength (such as extreme ultraviolet (EUV, wavelength 13.5nm), electron beam (E-Beam), etc.).

[0097] In some embodiments, the light used for exposure may be short wavelength light having a wavelength range of about 5 nm to 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.

[0098] In the step (eg, action or task) of forming a photoresist pattern, a negative type or negative-like pattern may be formed.

[0099] The exposed region of the photoresist layer has a solubility different from that of the unexposed region of the photoresist layer because a polymer is formed by a cross-linking reaction (eg, condensation between organometallic compounds).

[0100] 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 layer becomes difficult to dissolve in the developer.

[0101] 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 layer corresponding to the unexposed area.

[0102] The developer used in the method of forming a pattern according to one or more embodiments may be an organic solvent, such as one or more ketones (e.g., methyl ethyl ketone, acetone, cyclohexanone, and / or 2-heptanone), alcohols (e.g., 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, and / or methanol), esters (e.g., propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone), aromatic compounds (e.g., benzene, xylene, and / or toluene), and / or (e.g., any suitable) combinations thereof.

[0103] The photoresist pattern formed by exposing not only to light having a short wavelength such as i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm) or ArF excimer laser (wavelength 193nm) but also to light having high energy such as extreme ultraviolet (EUV, wavelength 13.5nm) or 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.

[0104] In addition, the half-pitch of the pitch of the photoresist pattern may be less than or equal to about 50 nm, for example, less than or equal to 40 nm, less than or equal to 30 nm, less than or equal to 20 nm, or less than or equal to 15 nm, and the line width roughness of the photoresist pattern may be less than or equal to about 10 nm, for example, 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.

[0105] The method of forming a pattern according to one or more embodiments 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 photoresist layer on the substrate, exposing the metal-containing photoresist layer, and developing the metal-containing photoresist layer using the aforementioned metal-containing resist developer composition.

[0106] The coating of the metal-containing resist composition on the substrate is the same as described above.

[0107] Removal of edge beads of metal-containing resists can be carried out by applying a suitable (e.g., well-known) organic solvent or a composition for removing edge beads in a suitable or suitable amount along the edge of the substrate while rotating the substrate at a suitable or suitable speed (e.g., 500 rpm or greater).

[0108] Drying and heating to form a metal-containing photoresist layer on the substrate are the same as described above.

[0109] The exposure of the metal-containing photoresist layer is the same as described above.

[0110] The photoresist pattern corresponding to the negative image can be completed by dissolving the photoresist layer corresponding to the unexposed area using the aforementioned developer composition of the metal-containing resist, and then removing the photoresist layer.

[0111] Hereinafter, a method of forming a pattern by developing is explained in more detail with reference to the accompanying drawings.

[0112] Figures 2 to 4 are cross-sectional views schematically showing a process sequence to explain a method of forming a pattern.

[0113] Reference Figure 2 , the exposed photoresist layer on the substrate 100 is developed to form a photoresist pattern 130P.

[0114] In one or more embodiments, the exposed photoresist layer may be developed to remove unexposed regions of the photoresist layer, and a photoresist pattern 130P including the exposed regions of the photoresist layer may be formed. The photoresist pattern 130P may include a plurality of openings OP.

[0115] In one or more embodiments, the development of the photoresist layer may be performed by a negative-tone development (NTD) process. Herein, the metal-containing photoresist developer composition according to one or more embodiments may be used as a developer composition.

[0116] Reference Figure 3 , using photoresist pattern 130P from Figure 2 The resulting feature layer 110 is shown for processing.

[0117] For example, the feature layer 110 is processed by one or more of the following suitable processes: etching the feature layer 110 exposed through the opening OP of the photoresist pattern 130P, implanting impurity ions into the feature layer 110, forming an additional film on the feature layer 110 through the opening OP, deforming a portion of the feature layer 110 through the opening OP (for example, removing a portion of the feature layer 110), and / or the like. Figure 3 An exemplary process of processing the feature pattern 110P by etching the feature layer 110 exposed through the opening OP is shown.

[0118] Reference Figure 4 ,from Figure 3 The result shown removes the photoresist pattern 130P remaining on the feature pattern 110P. To remove the photoresist pattern 130P, an ashing and stripping process may be used.

[0119] The method of forming a pattern according to one or more embodiments 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 layer on the substrate, exposing the metal-containing photoresist layer, and developing the metal-containing photoresist layer using the aforementioned developer composition of the metal-containing resist.

[0120] Each (e.g., action or task) step of the method is substantially the same as described above, but in the edge bead removal (e.g., action or task) step and the development (e.g., action or task) step, the composition for removing edge beads from a metal-containing resist or the developer composition of a metal-containing resist according to an embodiment of the present disclosure is used simultaneously (e.g., synchronously) to effectively improve the effect of removing edge beads and the solubility of unexposed areas, thereby meeting the need or expectation for processing and patterning smaller features, thereby achieving excellent or appropriate contrast characteristics, excellent or appropriate sensitivity, and reduced line edge roughness (LER).

[0121] Hereinafter, 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.

[0122] Preparation of a composition / developer composition for removing edge beads from metal-containing resists

[0123] Example 1

[0124] Difluoroacetic acid was mixed with propylene glycol methyl ether acetate (PGMEA) as a solvent in the composition shown in Table 1, and then the difluoroacetic acid was dissolved in PGMEA by shaking at room temperature (25° C.). Subsequently, the solution was filtered using a polytetrafluoroethylene (PTFE) filter having a pore size of 1 μm to obtain a final composition.

[0125] Examples 2 to 6 and Comparative Examples 1 and 2

[0126] Each composition was obtained in substantially the same manner as in Example 1, except that the above composition was respectively changed as shown in Table 1.

[0127] [Table 1]

[0128]

[0129] *DFAA: difluoroacetic acid

[0130] *DFPA: 2,2-difluoropropionic acid

[0131] *AA: Acetic acid

[0132] Preparation of photoresist composition containing organic metal

[0133] An organometallic compound having a structure of Chemical Formula C was dissolved in 4-methyl-2-pentanol at a concentration of 1 wt %, and then filtered using a 0.1 μm PTFE syringe filter, thereby preparing a photoresist composition.

[0134] [Chemical formula C]

[0135]

[0136] Evaluation: Evaluation of contrast performance and sensitivity

[0137] A metal-containing photoresist (PR) composition was spin-coated on an 8-inch wafer at a speed of 1,500 rpm for 30 seconds, and then heat-treated at 160° C. for 60 seconds to produce a coated wafer.

[0138] After the coated wafer was exposed to a dose of 10 mJ to 100 mJ in a 1.2 cm×0.9 cm rectangular pattern using a KrF scanner (PAS 5500 / 700D, ASML) and heat-treated at 160° C. for 90 seconds, the developer compositions according to Examples 1 to 6 and Comparative Examples 1 to 2 were applied thereto to develop them, and then, finally heat-treated at 2400° C. for 60 seconds, thereby obtaining a patterned wafer. The corresponding thickness of each exposure area of ​​the patterned wafer was measured to obtain Figure 5 The contrast curve shown in FIG. 1 is used to calculate the contrast performance (γ(contrast)) and sensitivity (D 100 ), and the results are provided in Table 2.

[0139] γ(contrast)=1 / log(D 100 / D0)

[0140] D 100 =Exposure dose when 100% PR remains

[0141] D0 = exposure dose when PR is completely removed

[0142] [Table 2]

[0143] γ(contrast) <![CDATA[Sensitivity (D 100 )]]> Example 1 443 20 Example 2 2409 20 Example 3 1625 29 Example 4 443 20 Example 5 1712 20 Example 6 1300 39 Comparative Example 1 463 29 Comparative Example 2 401 21

[0144] (*HP: based on half pitch), log(D 100 / D0) has a base of 10.

[0145] Figure 5 is a contrast curve obtained by measuring the thickness of each exposure area on each of the patterned wafers.

[0146] Reference Figure 5 , comparing the slopes of the contrast curves, Example 2 is shown to achieve much better or more suitable resolution.

[0147] In addition, the results of Table 2 indicate that if the metal-containing photoresist developer composition according to the example is applied, excellent or appropriate contrast performance and excellent or appropriate sensitivity characteristics are achieved as compared with the metal-containing photoresist developer composition according to the comparative example.

[0148] It will also be understood that the terms "includes / including" and / or "comprises / comprising" when used in this specification specify the presence of stated features, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, elements, components and / or groups thereof. The term "combination thereof" as used herein refers to a mixture, laminate, composite, copolymer, alloy, blend, reaction product, etc. of components.

[0149] As used herein, the terms "use", "using", and "used" may be considered synonymous with the terms "utilize", "utilizing", and "utilized", respectively. As used herein, expressions such as "at least one of", "one of", and "selected from" when preceding a series of elements modify the entire series of elements rather than modifying the individual elements in the series. For example, "at least one selected from a, b, and c", "at least one of a, b, or c", and "at least one of a, b, and / or c" may indicate including only a, only b, only c, including (e.g., simultaneously) both a and b, including (e.g., simultaneously) both a and c, including (e.g., simultaneously) both b and c, including all of a, b, and c, or variations thereof.

[0150] The use of "may" when describing embodiments of the inventive concept means "one or more embodiments of the inventive concept."

[0151] As used herein, the terms "about" and similar terms are used as terms of approximation rather than degree, and are intended to account for the inherent deviations in measured or calculated values ​​that one of ordinary skill in the art would recognize. As used herein, "about" includes the stated value and means within an acceptable range of deviations for the particular value as determined by one of ordinary skill in the art, taking into account the measurement in question and the errors associated with the measurement of a particular quantity (i.e., the limitations of the measurement system). For example, "about" may mean within one or more standard deviations, or within ±30%, 20%, 10%, 5% of the stated value.

[0152] In addition, any numerical range described herein is intended to include all sub-ranges of the same numerical precision that fall within the range. For example, a range of "1.0 to 10.0" is intended to include all sub-ranges between (and including) the minimum value 1.0 and the maximum value 10.0, i.e., having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as (for example) 2.4 to 7.6. Any maximum numerical limit described herein is intended to include all lower numerical limits that fall within it, and any minimum numerical limit described in this specification is intended to include all higher numerical limits that fall within it. Therefore, the applicant reserves the right to amend this specification (including the claims) to explicitly state any sub-ranges that fall within the range explicitly stated herein.

[0153] In the above, certain embodiments of the present disclosure have been described and illustrated, however, it is obvious to those skilled in the art that the present disclosure is not limited to the described embodiments, but various modifications and changes can be made without departing from the spirit and scope of the present disclosure. The description of the features or aspects in each embodiment should generally be considered to be applicable to other similar features or aspects in other embodiments. Therefore, it should be understood that the present disclosure is not limited to the disclosed embodiments, but on the contrary, it is intended to cover various modifications and equivalent arrangements within the spirit and scope of the appended claims and their equivalents.

Claims

1. A composition comprising: A C1 to C10 carboxylic acid compound substituted with at least one fluorine; and Organic solvents, The composition is used to remove edge beads from a metal-containing photoresist and / or is a developer composition for the metal-containing photoresist.

2. The composition according to claim 1, wherein The C1 to C10 carboxylic acid compound substituted with at least one fluorine is represented by Chemical Formula 1: [Chemical formula 1] in, In Chemical Formula 1, R 1 To R 3 are each independently hydrogen, fluorine, a fluorine-containing group, or a substituted or unsubstituted C1 to C5 alkyl group, n is an integer from 1 to 5, and R 1 To R 3 At least one of is fluorine or the fluorine-containing group.

3. The composition according to claim 2, wherein R 2 or R 3 At least one of is fluorine or the fluorine-containing group.

4. The composition according to claim 2, wherein R 2 and R 3 Each is independently fluorine or the fluorine-containing group.

5. The composition according to claim 2, wherein R 2 and R 3 are each independently fluorine.

6. The composition according to claim 1, wherein The C1 to C10 carboxylic acid compound substituted with at least one fluorine is at least one selected from difluoroacetic acid, 2,2-difluoropropionic acid, trifluoroacetic acid and monofluoroacetic acid.

7. The composition according to claim 1, wherein The composition comprises 0.01 wt % to 5 wt % of the C1 to C10 carboxylic acid compound substituted with at least one fluorine, and 95 wt % to 99.99 wt % of the organic solvent.

8. The composition according to claim 1, wherein The metal-containing photoresist includes at least one of an organic oxygen group-containing tin compound or an organic carbonyl oxygen group-containing tin compound.

9. The composition according to claim 1, wherein The metal-containing photoresist comprises a compound represented by Chemical Formula 2: [Chemical formula 2] in, In chemical formula 2, R 4 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, substituted or unsubstituted C6 to C30 aralkyl, 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, and R 5 To R 7 Each independently is: halogen; -OR b represents an alkoxy or aryloxy group, wherein R b is a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof; -O(CO)R 6 represents a carboxyl group, wherein R 6 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; -NR 7 R 8 An alkylamide or dialkylamide group represented by 7 and R 8 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; -NR 9 (CO)R 10 represents an amide group, wherein R 9 and R 10 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 -NR 11 C(NR 12 )R 13 represents an amidine group, wherein R 11 , R 12 and R 13 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.

10. A method for forming a pattern, the method comprising: coating a metal-containing photoresist composition on a substrate; Applying the composition according to any one of claims 1 to 9 along the edge of the substrate; Drying and heating to form a metal-containing photoresist layer on the substrate; exposing the metal-containing photoresist layer; as well as developing the metal-containing photoresist layer, wherein the composition is used to remove the edge bead from the metal-containing photoresist.

11. A method for forming a pattern, the method comprising: coating a metal-containing photoresist composition on a substrate; removing edge beads of metal-containing resist; Drying and heating to form a metal-containing photoresist layer on the substrate; exposing the metal-containing photoresist layer; as well as Developing the metal-containing photoresist layer using the composition as claimed in any one of claims 1 to 9, wherein the composition is the developer composition of the metal-containing photoresist.

12. A method for forming a pattern, the method comprising: coating a metal-containing photoresist composition on a substrate; Applying the composition according to any one of claims 1 to 9 along the edge of the substrate; Drying and heating to form a metal-containing photoresist layer on the substrate; exposing the metal-containing photoresist layer; as well as The metal-containing photoresist layer is developed using the composition according to any one of claims 1 to 9.

13. An edge bead removal composition for metal-containing photoresist, comprising the composition of claim 1.

14. A developer composition for a metal-containing photoresist, comprising the composition of claim 1.

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