Composition for removing edge beads from metal-containing resist, and method and system for forming patterns using the same

Abstract

A composition for removing edge beads from metal-containing resists includes an organic solvent, at least one alcohol compound selected from diol compounds and cyclic alcohol compounds, and an acid compound having a pKa1 of 1.0 < = pKa1 < = 4.5. In addition, methods and systems for forming patterns using the compositions are also provided.

Description

[0001] Cross-reference of related applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2024-0099696, filed with the Korean Intellectual Property Office on July 26, 2024, the entire contents of which are incorporated herein by reference. Technical Field

[0003] One or more embodiments of this disclosure relate to compositions for removing edge beads from metal-containing resists, and methods and systems for forming patterns using said compositions. Background Technology

[0004] In recent years, the critical dimensions in the semiconductor manufacturing industry have continued to shrink. This shrinkage requires new types of high-performance photoresist materials and patterning methods to meet the demands of processing and patterning increasingly smaller features.

[0005] Furthermore, with the rapid development of the semiconductor industry, the demand for semiconductor devices with faster operating speeds and larger storage capacities is increasing. To meet these requirements, process technologies aimed at improving the integration density, reliability, and response speed of semiconductor devices are being actively researched and developed. For example, accurately controlling and implanting impurities in the working regions of a semiconductor substrate (such as a silicon substrate) and interconnecting these regions to form devices and ultra-high-density integrated circuits is crucial. This can be achieved through photolithography processes, which involve coating a substrate with photoresist, selectively exposing it to ultraviolet (UV) light (including extreme ultraviolet (EUV)), electron beams, X-rays, and / or similar light sources, and then developing it.

[0006] In the process of forming a resist (i.e., photoresist) layer, the resist composition is typically applied to the substrate (such as a semiconductor substrate) while the substrate is being rotated. This process can result in resist being coated on the edges and back surfaces of the substrate, potentially causing particle or pattern defects in subsequent semiconductor processes (such as etching and ion implantation). Therefore, an edge bead removal (EBR) process is implemented to peel off and remove the resist from the edges and back surfaces of the substrate using a thinner composition. The EBR process requires a composition with excellent or suitable solubility for the resist (photoresist), capable of effectively removing the beads and any residual resist on the substrate without leaving any residue. Summary of the Invention

[0007] One or more aspects of embodiments of this disclosure relate to compositions for removing edge beads from metal-containing resists.

[0008] One or more aspects of embodiments of this disclosure relate to a method of forming patterns using the composition.

[0009] Other aspects will be set forth in part in the description below, and in part will be obvious from the description or may be learned by practicing the embodiments described in this disclosure.

[0010] According to one or more embodiments of the present disclosure, a composition for removing edge beads from a metal-containing resist comprises: an organic solvent, at least one alcohol compound selected from diol compounds and cyclic alcohol compounds, and an acid compound having a pKa1 of 1.0 ≤ pKa1 ≤ 4.5.

[0011] According to one or more embodiments of the present disclosure, a method of forming a pattern includes: coating a substrate with a metal-containing resist composition; coating along the edge of the substrate with a composition for removing edge beads from the metal-containing resist; drying and heating the resulting coating to form a metal-containing resist layer on the substrate; and exposing and developing the metal-containing resist layer to form a resist pattern.

[0012] According to one or more embodiments of the present disclosure, a system for forming a pattern includes: a tool for coating a metal-containing resist composition onto a substrate; a tool for coating along the edge of the substrate a composition for removing edge beads from the metal-containing resist; a tool for drying and heating the resulting coating to form a metal-containing resist layer on the substrate; and a tool for exposing and developing the metal-containing resist layer to form a resist pattern.

[0013] According to one or more embodiments, the composition for removing edge beads from metal-containing resists reduces the inherent metallic contamination in metal-containing resists and removes the resist coated on the substrate edge and back surface, thereby meeting the requirements for processing and patterning smaller features. Attached Figure Description

[0014] The accompanying drawings are included to provide a further understanding of this disclosure and are incorporated in and constitute a part of this disclosure. The drawings illustrate embodiments of the present disclosure and, together with the description, serve to explain the principles of the disclosure. The above and other aspects, features, and advantages of certain embodiments of the present disclosure will become more apparent when taken in conjunction with the accompanying drawings.

[0015] Figure 1 This is a schematic diagram of a photoresist coating apparatus according to one or more embodiments of the present disclosure.

[0016] Explanation of icon numbers

[0017] 1: Base support section

[0018] 2: Injection nozzle

[0019] 10: Photoresist solution

[0020] 12: Edge beads

[0021] W: Base Detailed Implementation

[0022] This disclosure can be modified in many alternative forms, and therefore specific embodiments will be illustrated and described in more detail in the accompanying drawings. However, it should be understood that this disclosure is not intended to be limited to the particular forms disclosed, but rather to cover all modifications, equivalents, and alternatives falling within the spirit and scope of this disclosure.

[0023] Hereinafter, embodiments of the present disclosure will be described in more detail with reference to the accompanying drawings. In the following description of the present disclosure, well-known suitable functions or structures will not be described in order to clarify the present disclosure.

[0024] For clarity of this disclosure, irrelevant descriptions and relationships are not provided, and throughout the disclosure, identical or similar configuration elements are indicated by the same reference numerals. Furthermore, since the size and thickness of each configuration shown in the figures are schematically illustrated for better understanding and ease of description, this disclosure is not necessarily limited thereto.

[0025] In the figures, the thickness of layers, films, panels, regions, and / or the like may be exaggerated for clarity. The thickness of portions of layers or regions and / or the like may also be exaggerated for clarity. It should be understood that if (for example, when) an element such as a layer, film, region, or substrate is referred to as "on" another element, it may be directly on or between the other element and an intervening element. Conversely, when an element is referred to as "directly on" another element, no intervening element is present between them.

[0026] In this disclosure, "substituted" means that hydrogen is replaced by a deuterium, halogen, hydroxyl, thiol, cyano, carbonyl, carboxyl, amino, amide, ester, substituted or unsubstituted C1 to C30 amino, nitro, substituted or unsubstituted C1 to C40 silyl, C1 to C30 alkyl, C1 to C10 haloalkyl, C1 to C10 alkylsilyl, C3 to C30 cycloalkyl, C6 to C30 aryl, C1 to C20 alkoxy, or C1 to C20 sulfide. "Unsubstituted" means that hydrogen remains hydrogen and is not replaced by another substituent.

[0027] In this disclosure, unless otherwise defined, "alkyl" refers to a straight-chain or branched aliphatic hydrocarbon group. Alkyl groups may be "saturated alkyl groups" that do not contain any double or triple bonds.

[0028] The alkyl group can be C1 to C20 alkyl. For example, the alkyl group can be C1 to C10 alkyl or C1 to C6 alkyl. For example, C1 to C5 alkyl refers to an alkyl chain containing 1 to 5 carbon atoms, and can be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, and sec-isopentyl.

[0029] Non-limiting examples of alkyl groups may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl and / or the like.

[0030] In the chemical formula described in this article, t-butyl refers to tert-butyl.

[0031] In this disclosure, unless otherwise defined, "cycloalkyl" refers to a monovalent cyclic aliphatic hydrocarbon group.

[0032] Cycloalkyl refers to cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl and / or similar compounds.

[0033] The cycloalkyl group can be C3 to C10 cycloalkyl, for example, C3 to C8 cycloalkyl, C3 to C7 cycloalkyl, or C3 to C6 cycloalkyl. For example, the cycloalkyl group can be cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl, but the embodiments of this disclosure are not limited thereto.

[0034] In this disclosure, unless otherwise defined, "heterocyclic alkyl" means a cycloalkyl group containing at least one heteroatom selected from N, O, S, P and Si.

[0035] In this disclosure, unless otherwise defined, "alkenyl" can be a straight-chain or branched aliphatic hydrocarbon group, and refers to an aliphatic unsaturated alkenyl group containing one or more carbon-carbon double bonds.

[0036] In this disclosure, unless otherwise defined, "alkynyl" can be a straight-chain or branched aliphatic hydrocarbon group and refers to an unsaturated alkynyl group containing one or more carbon-carbon triple bonds.

[0037] In this disclosure, "aryl" refers to all elements of a cyclic substituent having p orbitals that form a conjugation and may include monocyclic or fused polycyclic (i.e., rings sharing adjacent carbon atom pairs) functional groups.

[0038] For example, "heteroaryl" can refer to an aryl group containing at least one heteroatom selected from N, O, S, P, and Si. Two or more heteroaryl groups can be directly linked by σ bonds, or if (for example, when) the heteroaryl group contains two or more rings, the two or more rings can be fused. When the heteroaryl group is a fused ring, each ring can contain one to three heteroatoms.

[0039] For example, the substituted or unsubstituted C6 to C30 aryl groups may be substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthraquinone, substituted or unsubstituted phenanthyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted pyrene, substituted or unsubstituted biphenyl, substituted or unsubstituted p-terphenyl, substituted or unsubstituted meta-terphenyl, substituted or unsubstituted o-terphenyl, substituted or unsubstituted trefyl, substituted or unsubstituted benzophenone, substituted or unsubstituted triphenylene, substituted or unsubstituted peryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted indene, or combinations thereof (e.g., any suitable combination), but the embodiments of this disclosure are not limited thereto.

[0040] For example, substituted or unsubstituted C2 to C30 heterocyclic groups can be substituted or unsubstituted furanyl, substituted or unsubstituted thiophene, substituted or unsubstituted pyrrole, substituted or unsubstituted pyrazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted triazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted oxadiazolyl, substituted or unsubstituted thiadiazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophene, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted indole, or substituted or unsubstituted quinolinyl. The following are possible combinations of substituted or unsubstituted isoquinolinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxolinyl, substituted or unsubstituted naphthidyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridineyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted phenthiazinyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted carbazoyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted benzonaphthiophenyl, substituted or unsubstituted benzonaphthiophenyl, substituted or unsubstituted benzofuranfluorenyl, substituted or unsubstituted benzothiophenfluorenyl or (e.g., any suitable) combinations thereof, but the embodiments of this disclosure are not limited thereto.

[0041] Figure 1 This is a schematic diagram illustrating a photoresist coating apparatus according to one or more embodiments of the present disclosure.

[0042] Reference Figure 1The device is provided with a base support portion 1 on which the base W is placed. The base support portion 1 includes a spin chuck or a spin coater.

[0043] The substrate support portion 1 rotates in a first direction at a set or predetermined rotational speed to provide centrifugal force to the substrate W. A jet nozzle 2 may be disposed on the substrate support portion 1, and may be located in an air region away from the upper portion of the substrate W. During the solution supply phase, the nozzle 2 moves towards the upper portion of the substrate to jet the photoresist solution 10. Therefore, the photoresist solution 10 is coated onto the surface (e.g., the upper surface) of the substrate W by centrifugal force. Here, the photoresist solution 10 supplied to the center of the substrate W is coated while diffusing towards the edge of the substrate W under the action of centrifugal force, with a portion of the photoresist solution 10 moving to the side surfaces and the lower surfaces of the edges of the substrate W.

[0044] For example, in one or more embodiments, in the coating process, the photoresist solution 10 may be coated primarily by spin coating, wherein a set or predetermined amount of the viscous photoresist solution 10 is supplied to the central portion of the substrate W and gradually diffuses towards the edge of the substrate W by centrifugal force.

[0045] Therefore, the resist layer is formed uniformly by the rotation speed of the substrate support portion.

[0046] In one or more embodiments, this rotation causes the solvent in the photoresist solution to evaporate, thereby gradually increasing the viscosity, resulting in a relatively large amount of photoresist accumulating at the substrate edge under the action of surface tension, and even, in severe cases, accumulating on the lower surface of the substrate edge, which is referred to in this disclosure as edge beads 12.

[0047] The following describes in more detail a composition for removing edge beads from a metal-containing resist according to one or more embodiments. In this disclosure, unless otherwise stated, the term "resist" may be used interchangeably with the term "photoresist".

[0048] According to one or more embodiments of the present disclosure, a composition for removing edge beads from a metal-containing resist may include: an organic solvent; at least one alcohol compound selected from diol compounds and cyclic alcohol compounds; and an acid compound having a pKa1 of 1.0 ≤ pKa1 ≤ 4.5.

[0049] Compositions for removing edge beads from metal-containing resists may include cyclic compounds substituted with hydroxyl (-OH) groups. Since the hydroxyl (-OH) groups form coordination bonds with the metal-containing resists, the metal-containing resists can be effectively removed by applying a composition containing said compounds.

[0050] In one or more embodiments, the diol compound may be represented by chemical formula 1 or chemical formula 2.

[0051] Chemical Formula 1 Chemical Formula 2

[0052]

[0053] In chemical formula 1 and chemical formula 2,

[0054] R 1 To R 10 Each can be independently hydrogen, halogen, hydroxyl, amino, nitro, substituted or unsubstituted C1 to C30 amino, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C20 aryl.

[0055] From R 1 To R 5 One of the selected components is the hydroxyl group.

[0056] From R 6 To R 10 One of the selected components is a hydroxyl group, and

[0057] n can be an integer from 1 to 10.

[0058] In one or more embodiments, the diol compound represented by Formula 1 may be represented by Formula 1-1.

[0059] Chemical Formula 1-1

[0060]

[0061] In one or more embodiments, the diol compound represented by Formula 2 may be represented by any one of Formulas 2-1 to 2-3.

[0062] Chemical Formula 2-1 Chemical Formula 2-2 Chemical Formula 2-3

[0063]

[0064] In chemical formulas 1-1 and 2-1 to 2-3,

[0065] R 1 To R 4 R 6 To R 10 The definitions of and n can be independently identical to those described in this article.

[0066] In one or more embodiments, the cyclic alcohol compound may be represented by chemical formula 3.

[0067] Chemical formula 3

[0068]

[0069] In chemical formula 3,

[0070] R 11 To R 16 Each of these groups can be independently hydrogen, halogen, hydroxyl, amino, nitro, substituted or unsubstituted C1 to C30 amino, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C20 aryl, and

[0071] From R 11 To R 16 At least one of the selected components is a hydroxyl group.

[0072] In one or more embodiments, the cyclic alcohol compound represented by Formula 3 may be represented by any one of Formulas 3-1 to 3-3.

[0073] Chemical Formula 3-1 Chemical Formula 3-2 Chemical Formula 3-3

[0074]

[0075] In chemical formulas 3-1 to 3-3

[0076] R 11 To R 16 The definitions can be independently identical to those described in this article.

[0077] In one or more embodiments, the alcohol compound may include (for example) at least one of pyrocatechol, 4-methylcatechol, 4-chlorocatechol, 4-nitrocatechol, cycloheptatrienolone, 1,2-ethylene glycol and / or (for example, any suitable) combinations thereof.

[0078] In one or more embodiments, the pKa1 of the acid compound may be 1.0 ≤ pKa1 ≤ 4.0.

[0079] The acid compound may be at least one of the following: phosphoric acid, phosphonic acid, methylphosphonic acid, ethylphosphonic acid, butylphosphonic acid, hexylphosphonic acid, n-octylphosphonic acid, tetradecylphosphonic acid, octadecylphosphonic acid, phenylphosphonic acid, vinylphosphonic acid, 6-hydroxyhexylphosphonic acid, decylphosphonic acid, methylene diphosphonic acid, tamidotrimethylene triphosphonic acid, diphenylphosphonic acid, bis(4-methoxyphenyl)phosphonic acid, phosphonic acid, bis(hydroxymethyl)phosphonic acid, phenylphosphonic acid, p-(3-aminopropyl)-p-butylphosphonic acid, chloroacetic acid, formic acid, acetic acid, or any suitable combination thereof.

[0080] In one or more embodiments, the acid compound may be at least one of the following: phosphoric acid, phosphonic acid, methylphosphonic acid, butylphosphonic acid, phenylphosphonic acid, vinylphosphonic acid, chloroacetic acid, formic acid, acetic acid, or any suitable combination thereof.

[0081] In one or more embodiments, based on 100% by weight of the total weight of the composition, the composition for removing edge beads from metal-containing resists may include: about 0.05 to about 40% by weight of alcohols and acids; and about 60 to about 99.95% by weight of organic solvents.

[0082] Within the above range, the amount may include (e.g., about 0.1 to about 40% by weight) alcohols and acid compounds.

[0083] The weight ratio can be from about 1:0.5 to about 1:50, including alcohols and acids.

[0084] For example, in one or more embodiments, alcohols and acids may be included in a weight ratio of about 1:1 to about 1:50 (e.g., a weight ratio of about 1:1 to about 1:40 or about 1:1 to about 1:30).

[0085] Within the above range, alcohol compounds may be included in amounts less than about 10% by weight (e.g., less than about 9% by weight or less than about 8% by weight).

[0086] Within the aforementioned range, acid compounds may be included in amounts less than about 40% by weight (e.g., in amounts less than or equal to about 35% by weight or in amounts less than or equal to about 30% by weight).

[0087] According to one or more embodiments, non-limiting examples of organic solvents included in the composition for removing edge beads from metal-containing resists may include 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, dipropylene glycol dimethyl ether, ethanol, 2-butoxyethanol, n-propanol, isopropanol, n-butanol, isobutanol, hexanol, ethylene glycol, propylene glycol, etc. Heptanone, propylene carbonate, butyl carbonate, diethyl ether, dibutyl ether, ethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diisopentyl 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, cyclohexanone, methyl 2-hydroxy-2-methylpropionate (HBM), γ- 1-Butyrolactone (GBL), 1-Butanol, Ethyl lactate (EL), Diallyl ether (DBE), Diisopropyl ether (DIAE), Acetylacetone, 4-Methyl-2-pentanol (also described as methyl isobutyl methanol (MIBC)), 1-Methoxy-2-propanol, 1-Ethoxy-2-propanol, Toluene, Cyclopentanone, Cyclohexanone, Ethyl 2-hydroxypropionate, Ethyl 2-hydroxy-2-methylpropionate, Ethyl ethoxylate, Ethyl hydroxyacetate, Methyl 2-hydroxy-3-methylbutyrate, Methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, Ethyl 3-ethoxypropionate, Methyl 3-ethoxypropionate, Ethyl pyruvate, Ethyl pyruvate, Ethyl acetate, Butyl acetate, Butyl lactate, Methyl 2-hydroxyisobutyrate, Methoxybenzene, n-Butyl acetate, 1-Methoxy-2-propyl acetate, Methoxyethoxypropionate, Ethoxyethoxypropionate, and / or mixtures thereof (e.g., any suitable).

[0088] According to one or more embodiments of the present disclosure, the composition for removing edge beads from metal-containing resists can effectively remove metal-containing resists, such as unwanted metal residues, like tin-based metal residues.

[0089] In cases where other additives are included (e.g., in the examples), the balance of the contained components other than the organic solvent may include the organic solvent.

[0090] In one or more embodiments, the composition may further include at least one other additive selected from surfactants, dispersants, hygroscopic agents and coupling agents.

[0091] According to one or more embodiments of this disclosure, a method of forming a pattern may include removing edge beads using a composition for removing edge beads from a metal-containing resist. For example, in one or more embodiments, the pattern manufactured / formed may be a photoresist pattern. In one or more embodiments, it may be a negative (type) photoresist pattern.

[0092] A method for forming a pattern according to one or more embodiments may include: coating a metal-containing resist composition onto a substrate, coating (e.g., applying) a composition along the edge of the substrate for removing edge beads from the metal-containing resist, drying and heating the resulting coating to form a metal-containing resist layer on the substrate, and exposing and developing the metal-containing resist layer to form a resist pattern.

[0093] For example, patterning using a metal-containing resist composition may include coating a substrate on which a thin film has been formed by spin coating, slot coating, inkjet printing, and / or similar methods, and drying the coated metal-containing resist composition to form a photoresist layer. The metal-containing resist composition may include tin compounds, for example, at least one of tin compounds containing an organooxy group or an organocarbonyloxy group.

[0094] For example, in one or more embodiments, the metal compound contained in the metal-containing resist composition may be represented by chemical formula 4.

[0095] Chemical Formula 4

[0096]

[0097] In chemical formula 4,

[0098] R 17 The following can be selected: 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 substituted or unsubstituted C7 to C30 aralkyl.

[0099] R 18 To R 20 Each of these can be independently 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, a substituted or unsubstituted C7 to C30 aralkyl, an alkoxy, or an aryloxy (-OR) b , where R b It can be 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 (e.g., any suitable combination thereof), or a carboxyl group (-O(CO)R). c, where R c It may 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 or any suitable combination thereof, alkylamino or dialkylamino (-NR) d R e , where R d and R e Each of these can be independently hydrogen, 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 any suitable combination thereof, or an amide group (-NR). f (COR g ), where R f and R g Each of these can be independently hydrogen, 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 any suitable combination thereof, and an amidoyl (-NR) group. h C(NR i )R j , where R h R i and R j Each of these can be independently hydrogen, 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 any suitable combination thereof, alkylthio or arylthio (-SR). k , where R k It can be 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 any suitable combination thereof) or a thiocarboxyl (-S(CO)R) l , where R lIt can 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, or any suitable combination thereof, and

[0100] R 18 To R 20 Choose at least one from the following: alkoxy or aryloxy (-OR) b , where R b It can be 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 (e.g., any suitable combination thereof), or a carboxyl group (-O(CO)R). c , where R c It may 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 or any suitable combination thereof, alkylamino or dialkylamino (-NR) d R e , where R d and R e Each of these can be independently hydrogen, 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 any suitable combination thereof, or an amide group (-NR). f (COR g ), where R f and R g Each of these can be independently hydrogen, 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 any suitable combination thereof, and an amidoyl (-NR) group. h C(NR i )R j , where R h R i and R jEach of these can be independently hydrogen, 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 any suitable combination thereof, alkylthio or arylthio (-SR). k , where R k It can be 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 (e.g., any suitable combination thereof), and a thiocarboxyl (-S(CO)R) l , where R l It may 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, or any suitable combination thereof.

[0101] In one or more embodiments, the metal compound contained in the metal-containing resist composition may be represented by chemical formula 5 or chemical formula 6.

[0102] Chemical formula 5

[0103] R 21 z SnO (2-(z / 2)-(x / 2)) (OH) x

[0104] In chemical formula 5,

[0105] R 21 It can be a C1 to C31 hydrocarbon group, 0 < z ≤ 2, and 0 < (z+x) ≤ 4>;

[0106] Chemical Formula 6

[0107] R 22 p Sn q X l Y k

[0108] In chemical formula 6,

[0109] R 22It may be 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 aliphatic unsaturated organogroup containing one or more double or triple bonds, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a carbonyl group, an ethylene oxide group, an propylene oxide group, or any combination thereof (e.g., any suitable combination).

[0110] X can be sulfur (S), selenium (Se), or tellurium (Te).

[0111] Y can be -OR m or -OC(=O)R n ,

[0112] Where R m It may be 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 any suitable combination thereof.

[0113] R n It may 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, or any suitable combination thereof, and

[0114] p, q, l, and k can each be an integer from 1 to 20 independently.

[0115] In one or more embodiments, the composition for removing edge beads from metal-containing resists can be applied (e.g., applied) while rotating the substrate at a suitable or appropriate speed (e.g., 500 revolutions per minute or higher).

[0116] Subsequently, a first heat treatment process is performed on the substrate on which the resist layer is formed, by heating it. The first heat treatment process can be performed at a temperature of about 80°C to about 120°C, in which the solvent evaporates and the resist layer can adhere more firmly to the substrate.

[0117] Then, the resist layer is selectively exposed.

[0118] For example, examples of light that can be used in an exposure process include not only light such as i-line (wavelength 365 nanometers (nm)), KrF excimer laser (wavelength 248 nanometers) or ArF excimer laser (wavelength 193 nanometers), but also EUV (light with high-energy wavelengths, such as EUV (extreme ultraviolet, wavelength 13.5 nanometers)), electron beam (E-Beam) and / or similar light.

[0119] For example, the light used for exposure according to one or more embodiments may be light having a wavelength range of about 5 nanometers to about 150 nanometers or light having a high-energy wavelength, such as EUV (extreme ultraviolet, wavelength 13.5 nanometers) or electron beam (E-Beam) and / or similar light.

[0120] When forming a resist pattern, a negative (type) pattern can be formed.

[0121] Because polymers are formed in the exposed areas through cross-linking reactions such as condensation between organometallic compounds, the exposed areas of the resist layer have different solubility than the unexposed areas of the resist layer.

[0122] Then, a second heat treatment process is performed on the substrate. This second heat treatment process can be performed at a temperature of approximately 90°C to approximately 200°C. By performing the second heat treatment process, the exposed areas of the resist layer become less likely to dissolve in the developer.

[0123] For example, in one or more embodiments, a photoresist pattern corresponding to a negative image can be completed by using an organic solvent such as 2-heptanone to dissolve and remove the resist layer corresponding to the unexposed area.

[0124] The developer used in the pattern forming method according to one or more embodiments may be an organic solvent, non-limiting examples of which may include: ketones, such as methyl ethyl ketone, acetone, cyclohexanone and / or 2-heptanone; alcohols, such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol and / or methanol; esters, such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone; aromatic compounds, such as benzene, xylene and / or toluene, and / or combinations thereof (e.g., any suitable).

[0125] In one or more embodiments, the method of forming a pattern may further include coating (e.g., applying) a composition for removing edge beads from the metal-containing resist after exposure and development processes. For example, in one or more embodiments, it may include coating (e.g., applying) an appropriate amount of the composition for removing edge beads from the metal-containing resist along the edge of the substrate while rotating the substrate at an appropriate or suitable speed (e.g., 500 rpm or higher).

[0126] As described above, photoresist patterns formed by exposure to light having wavelengths such as i-lines (365 nm), KrF excimer lasers (248 nm), ArF excimer lasers (193 nm), or EUV (extreme ultraviolet; 13.5 nm), or high-energy light (such as electron beams (E-beams)), can have widths of about 5 nm to about 100 nm. For example, in one or more embodiments, the photoresist patterns can be formed to have widths of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm.

[0127] In one or more embodiments, the photoresist pattern may have a pitch of less than or equal to about 50 nanometers (e.g., less than or equal to 40 nanometers, e.g., less than or equal to 30 nanometers, e.g., less than or equal to 20 nanometers, or e.g., less than or equal to 15 nanometers) and a linewidth roughness of less than or equal to about 10 nanometers, less than or equal to about 5 nanometers, less than or equal to about 3 nanometers, or less than or equal to about 2 nanometers.

[0128] The present disclosure will now be described in more detail through examples relating to the preparation of compositions for removing edge beads from metal-containing resists. However, the technical features of the present disclosure are not limited to the examples described below.

[0129] Preparation Example: Preparation of Photoresist Compositions Containing Organometallic Compounds

[0130] An organometallic compound having a structural unit with the chemical formula C was dissolved in 4-methyl-2-pentanol at a concentration of 1% by weight, and then filtered through a 0.1 μm PTFE syringe filter to prepare a photoresist composition.

[0131] Chemical formula C

[0132]

[0133] Examples and Comparative Examples: Preparation of Compositions for Removing Edge Beads

[0134] The alcohol, acid, and organic solvent were mixed according to the combinations shown in Table 1, and then stirred at room temperature (25°C) to completely dissolve. The mixture was then filtered through a PTFE filter with a pore size of 1 μm to obtain the final composition.

[0135] Table 1

[0136]

[0137] PGMEA: Propylene Glycol Methyl Ether Acetate

[0138] PGME: Propylene Glycol Methyl Ether

[0139] MIBC: Methyl isobutyl alcohol

[0140] PEP: (PGMEA : PGME = 7 : 3 (w / w)) mixed solvent

[0141] Evaluation 1: Evaluation of residual film thickness (peel test) and evaluation of Sn residue before development

[0142] 1.0 mL of a photoresist composition containing an organometallic compound, prepared according to the preparation example, was poured onto a 6-inch silicon wafer, left to stand for 20 seconds, and then spin-coated at 800 rpm for 30 seconds. The resulting resist layer, after heat treatment at 200°C for 60 seconds, was then measured using elliptic polarization. On the silicon wafer with the resist layer formed, 10 mL of one of the compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 5 for removing edge beads was injected along the edge, spin-coated for 5 seconds, and then dried by spin drying at 1,500 rpm. The film thickness, obtained after heat treatment at 150°C for 60 seconds, was then remeasured using elliptic polarization to confirm the thickness change before and after the edge bead removal process, and evaluated according to the following criteria. Furthermore, vapor phase decomposition-inductively coupled plasma-mass spectrometry (VPD ICP-MS) analysis was performed to confirm the Sn residue; the results are shown in Table 2.

[0143]

[0144] If the residual thickness is less than 5 Å: ○;

[0145] If the residual thickness is greater than 5 Å: X

[0146] Evaluation 2: Visual evaluation of surface stains

[0147] As in Evaluation 1, after the edge bead removal process, the surface contaminants on the wafer coated with the resist layer were inspected using a KMAC-ST400DLX instrument. Simultaneously, before and after the final baking at 150°C for 60 seconds, the contaminants on the substrate-back surface were visually inspected. The evaluation criteria are as follows:

[0148]

[0149] No stains before / after baking: ○;

[0150] Stains remained but disappeared after baking: △;

[0151] Stains after baking: X

[0152] Table 2

[0153]

[0154] Referring to Table 2, the composition for removing edge beads from metal-containing resist according to the examples has a superior metal removal effect compared to the composition for removing edge beads from metal-containing resist according to the comparative examples, thereby further promoting the reduction of residual metal.

[0155] Here it should be understood that terms such as “comprising,” “including,” or “having” are intended to specify the presence of a feature, quantity, step, element, or combination thereof in an implementation, but do not preclude the possibility of the presence or addition of one or more other features, quantities, steps, elements, or combinations thereof.

[0156] In the context of this disclosure, unless otherwise defined, the term "use" may be considered synonymous with the term "utilize".

[0157] As used herein, the singular forms "a," "an," and "described" are intended to include the plural forms unless the context clearly indicates otherwise. Furthermore, the word "may" used in describing embodiments of this disclosure may refer to "one or more embodiments of this disclosure." Additionally, as used herein, the term "and / or" includes any and all combinations of the related listed items. The " / " used herein may be interpreted as "and" or "or," depending on the context. When preceding a list of elements, expressions such as "at least one," "one of," and "selected from" modify the entire list of elements without modifying any individual element in the list. For example, "at least one of a, b, or c," "at least one of a, b, and / or c," "at least one selected from a, b, and c," "at least one selected from a to c," etc., may indicate only a, only b, only c, both a and b (e.g., simultaneously), both a and c (e.g., simultaneously), both b and c (e.g., simultaneously), all a, b, and c, or variations thereof.

[0158] In this disclosure, although the terms "first," "second," etc., may be used to describe one or more elements, components, regions, and / or layers, these elements, components, regions, and / or layers should not be limited by these terms. These terms are used only to distinguish one component from another.

[0159] As used herein, the terms “substantially,” “approximately,” and similar terms are used as approximate terms rather than terms of degree, intended to take into account the inherent biases in measurements or calculations as recognized by one of ordinary skill in the art.

[0160] Any numerical range described herein is intended to include all subranges with the same numerical precision contained within the range. For example, the range "1.0 to 10.0" is intended to include all subranges between (and including) the minimum value of 1.0 and the maximum value of 10.0, i.e., a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as 2.4 to 7.6. Any maximum numerical limit described herein is intended to include all lower numerical limits contained therein, and any minimum numerical limit described in this specification is intended to include all higher numerical limits contained therein. Therefore, the applicant reserves the right to amend this specification (including the claims) to expressly represent any subranges contained within the ranges expressly stated herein.

[0161] The pattern forming system or apparatus according to the embodiments of the invention described herein, and / or any other related apparatus or components, may be implemented using any suitable hardware, firmware (e.g., application-specific integrated circuits), software, or a combination of software, firmware, and hardware. For example, various components of the apparatus may be formed on an integrated circuit (IC) chip or on a separate IC chip. Furthermore, various components of the apparatus may be implemented on a flexible printed circuit film, a tape carrier package (TCP), a printed circuit board (PCB), or formed on a substrate. Additionally, various components of the apparatus may be processes or threads running on one or more processors in one or more computing devices, executing computer program instructions and interacting with other system components to perform the various functions described herein. The computer program instructions are stored in memory, which may be implemented in the computing device using standard storage devices (e.g., random access memory (RAM)). The computer program instructions may also be stored on other non-transitory computer-readable media, such as CD-ROMs, flash drives, or similar devices. Furthermore, those skilled in the art will recognize that the functions of various computing devices may be combined or integrated into a single computing device, or the functions of a particular computing device may be distributed across one or more other computing devices, without departing from the scope of this disclosure.

[0162] Those skilled in the art will understand from the entire contents of this disclosure that each suitable feature of the various embodiments of this disclosure may be combined or integrated with each other, in whole or in part, and may be technically interlocked and operated in various suitable manners. Each embodiment may be implemented independently or in any suitable manner in combination with each other, unless otherwise stated or implied.

[0163] Prior to this, certain embodiments have been described and illustrated. However, it will be apparent to those skilled in the art that this disclosure is not limited to the described exemplary embodiments, and various modifications and transformations can be made without departing from the spirit and scope of this disclosure. Therefore, these modified or transformed embodiments should not be understood separately from the technical concept and aspects of this disclosure, and the modified embodiments are within the scope of the claims of this disclosure and their equivalents.

Claims

1. A composition for removing edge beads from a metal-containing resist, comprising: Organic solvents; One or more alcohol compounds selected from diols and cyclic alcohols; as well as Acid compounds with a pKa1 of 1.0 ≤ pKa1 ≤ 4.

5.

2. The composition according to claim 1, wherein... The diol compound 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 10 Each of these groups is independently hydrogen, halogen, hydroxyl, amino, nitro, substituted or unsubstituted C1 to C30 amino, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C20 aryl. From R 1 To R 5 One of them was selected as a hydroxyl group. From R 6 To R 10 One of them was selected as hydroxyl, and n is an integer from 1 to 10.

3. The composition according to claim 2, wherein... The diol compound represented by chemical formula 1 is represented by chemical formula 1-1, and The diol compound represented by chemical formula 2 is represented by any one of chemical formulas 2-1 to 2-3: Chemical Formula 1-1 Chemical Formula 2-1 Chemical Formula 2-2 Chemical Formula 2-3 In chemical formulas 1-1 and 2-1 to 2-3, R 1 To R 4 And n are the same as those defined in Chemical Formula 1, and R 6 To R 10 Each is the same as defined in chemical formula 2.

4. The composition according to claim 1, wherein... The cyclic alcohol compound is represented by chemical formula 3: Chemical formula 3 In chemical formula 3, R 11 To R 16 Each of the following groups is independently hydrogen, halogen, hydroxyl, amino, nitro, substituted or unsubstituted C1 to C30 amino, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C20 aryl, and From R 11 To R 16 At least one of the selected components is a hydroxyl group.

5. The composition according to claim 4, wherein... The cyclic alcohol compound represented by chemical formula 3 is represented by any one of chemical formulas 3-1 to 3-3: Chemical Formula 3-1 Chemical Formula 3-2 Chemical Formula 3-3 In chemical formulas 3-1 to 3-3 R 11 To R 16 Each is the same as defined in chemical formula 3.

6. The composition according to claim 1, wherein... The alcohol compounds include at least one of the following: pyrocatechol, 4-methylcatechol, 4-chlorocatechol, 4-nitrocatechol, cycloheptatrienolone, 1,2-ethylene glycol, or combinations thereof.

7. The composition according to claim 1, wherein The pKa1 of the acid compound is 1.0 ≤ pKa1 ≤ 4.

0.

8. The composition according to claim 1, wherein The acid compound comprises at least one of the following: phosphoric acid, phosphonic acid, methylphosphonic acid, ethylphosphonic acid, butylphosphonic acid, hexylphosphonic acid, n-octylphosphonic acid, tetradecylphosphonic acid, octadecylphosphonic acid, phenylphosphonic acid, vinylphosphonic acid, 6-hydroxyhexylphosphonic acid, decylphosphonic acid, methylene diphosphonic acid, methyltrimethylamine triphosphonic acid, diphenylphosphonic acid, bis(4-methoxyphenyl)phosphonic acid, phosphonic acid, bis(hydroxymethyl)phosphonic acid, phenylphosphonic acid, p-(3-aminopropyl)-p-butylphosphonic acid, chloroacetic acid, formic acid, acetic acid, or combinations thereof.

9. The composition according to claim 1, wherein Based on the total weight of the composition (100% by weight), the alcohol compound and the acid compound are 0.05% to 40% by weight, and Based on 100% by weight of the total weight of the composition, the organic solvent is 60 to 99.95% by weight.

10. The composition according to claim 1, wherein The weight ratio of the alcohol compound to the acid compound is from 1:0.5 to 1:

50.

11. The composition according to claim 1, wherein The metal-containing resist includes one or more tin compounds selected from tin compounds containing organic oxygen groups and tin compounds containing organic carbonyl oxygen groups.

12. The composition according to claim 11, wherein The tin compound is represented by chemical formula 4: Chemical Formula 4 ,and in, In chemical formula 4, R 17 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 substituted or unsubstituted C7 to C30 aralkyl. R 18 To R 20 Each of the following is independently 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; a substituted or unsubstituted C7 to C30 aralkyl; or derived from -OR b The alkoxy or aryloxy group represents R. b It 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; derived from -O(CO)R c The carboxyl group represents R. c It is hydrogen, 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; derived from -NR d R e The alkylamino or dialkylamino group represents R. d and R e Each is independently hydrogen, 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; and is composed of -NR f (COR g ) represents an amide group, where R f and R g Each is independently hydrogen, 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; and is composed of -NR h C(NR i )R j The amidine group is represented by R. h R i and R j Each is independently hydrogen, 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; derived from -SR k The alkyl thio group or aryl thio group represents R. k It 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; or it is composed of -S(CO)R l The thiocarboxyl group represents R. l It is hydrogen, 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. R 18 To R 20 Choose at least one from the following: by -OR b The alkoxy or aryloxy group represents R. b It 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; derived from -O(CO)R c The carboxyl group represents R. c It is hydrogen, 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; derived from -NR d R e The alkylamino or dialkylamino group represents R. d and R e Each is independently hydrogen, 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; and is composed of -NR f (COR g ) represents an amide group, where R f and R g Each is independently hydrogen, 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; and is composed of -NR h C(NR i )R j The amidine group is represented by R. h R i and R j Each is independently hydrogen, 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; derived from -SR k The alkyl thio group or aryl thio group represents R. k It 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; and derived from -S(CO)R l The thiocarboxyl group represents R. l It 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.

13. The composition according to claim 11, wherein The tin compound is represented by chemical formula 5 or chemical formula 6: Chemical formula 5 R 21 z SnO (2-(z / 2)-(x / 2)) (OH) x in, In chemical formula 5, R 21 It is a C1 to C31 hydrocarbon group, 0 < z ≤ 2, and 0 < (z+x) ≤ 4; Chemical Formula 6 R 22 p Sn q X l Y k In chemical formula 6, R 22 It 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 aliphatic unsaturated organic group containing one or more double or triple bonds, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a carbonyl group, an ethylene oxide group, an propylene oxide group, or a combination thereof. X is sulfur, selenium, or tellurium. Y is – OR m or -OC(=O)R n , Where R m It 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. R n It is hydrogen, 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, and p, q, l, and k are each an independent integer from 1 to 20.

14. A method for forming a pattern, comprising: A metal-containing resist composition is coated onto a substrate; The composition of claim 1 is coated along the edge of the substrate; The resulting coating is dried and heated to form a metal-containing resist layer on the substrate; and The metal-containing resist layer is exposed and developed to form a resist pattern.

15. A system for forming patterns, comprising: Tools for coating a metal-containing resist composition onto a substrate; A tool for coating the composition of claim 1 along the edge of the substrate; A tool for drying and heating the resulting coating to form a metal-containing resist layer on the substrate; as well as A tool used to expose and develop the metal-containing resist layer to form a resist pattern.

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