Composition for removing edge beads of metal-containing photoresists or developer composition for metal-containing photoresists, and method for forming patterns using the same

Abstract

To provide a composition for removing edge beads of metal-containing photoresist having excellent sensitivity and LER characteristics or a developer composition for metal-containing photoresist, and a method for forming pattern using the same.SOLUTION: There is provided a composition for removing edge beads of metal-containing photoresists, which is substantially free of water, and which includes at least one additive selected from an amino acid-based compound, a sulfur-containing acid compound, and a sulfur-containing amine-based compound, and an organic solvent. or a developer composition for metal-containing photoresists. And there is also provided a method for forming patterns using the same.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a composition for removing edge beads of a metal-containing photoresist or a developer composition for a metal-containing photoresist, and a pattern forming method using the same. [Background technology]

[0002] In recent years, the semiconductor industry has been continuously shrinking its critical dimensions, which has led to the demand for new types of high-performance photoresist materials and patterning methods to meet the demands of processing and patterning smaller and smaller features.

[0003] In addition, with the recent rapid development of the semiconductor industry, semiconductor devices are required to have excellent operating speeds and large-capacity memory capabilities, and in response to such demands, process technologies for improving the integration, reliability, and response speed of semiconductor devices are being developed. In particular, it is important to precisely control / inject impurities into the active regions of a silicon substrate, interconnect these regions, and directly form elements and ultra-high density circuits, which can be achieved by a photolithography process. That is, it is becoming important to consider the integration of the photolithography process, which includes coating a photoresist on a substrate, selectively exposing it to ultraviolet light (including extreme ultraviolet light), electron beams, or X-rays, and then developing it.

[0004] In particular, in the process of forming a photoresist layer, photoresist is applied onto the substrate while rotating the silicon substrate, and in this process, photoresist is also applied to the edge and back surface of the substrate, which may cause pattern defects in subsequent processes of semiconductor manufacturing, such as etching and ion implantation processes. Therefore, a process of stripping and removing the photoresist applied to the edge and back surface of the silicon substrate using a thinner composition, i.e., an edge bead removal (EBR) process, is performed. The EBR process requires a composition that has excellent solubility in photoresist and effectively removes beads and photoresist remaining on the substrate without generating photoresist residues.

[0005] In addition, there is a need to develop a photoresist that can guarantee excellent etching resistance and resolution in the photolithography process while improving sensitivity and CD (critical dimension) uniformity and improving LER (line edge roughness) characteristics, as well as a developer composition that can achieve this. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2016-170337 A [Patent Document 2] Patent No. 5288144 [Patent Document 3] Korean Patent Publication No. 2012-0078607 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a composition for removing edge beads of a metal-containing photoresist or a developer composition for a metal-containing photoresist, which has excellent sensitivity and LER properties.

[0008] A further object of the present invention is to provide a pattern forming method utilizing the above composition. [Means for solving the problem]

[0009] The composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist according to the present invention is substantially free of water and contains at least one additive selected from an amino acid-based compound, a sulfur-containing acid compound, and a sulfur-containing amine-based compound, and an organic solvent.

[0010] The water content of the composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist may be 1,000 ppm or less.

[0011] The amino acid compound may be at least one of the compounds represented by the following Chemical Formulas 1 to 3.

[0012] [ka]

[0013] In the above Chemical Formulas 1 to 3, L 1 each independently represents a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, X 1 are each independently a single bond, O, S, or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, R is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; R 1 ~R 7each independently represents a hydrogen atom, a hydroxy group, a mercapto group, an amino group, an amido group, a guanidino group, a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, n is an integer of 0 or 1.

[0014] The amino acid compound may be at least one of alanine, glycine, valine, leucine, isoleucine, proline, methionine, phenylalanine, tyrosine, tryptophan, serine, threonine, cysteine, asparagine, glutamine, aspartic acid, glutamic acid, histidine, lysine, arginine, and N-methylcysteine.

[0015] The sulfur-containing acid compound may be at least one of compounds represented by the following Formula 4 and Formula 5.

[0016] [ka]

[0017] In the above Chemical Formula 4 and Chemical Formula 5, L 2 and L 3 each independently represents a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, R 8 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, R 9is a sulfur-containing substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a sulfur-containing substituted or unsubstituted heterocycloalkyl group having 3 to 10 carbon atoms, a sulfur-containing substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a sulfur-containing substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

[0018] The sulfur-containing acid compound may be at least one compound selected from the compounds listed in Group 1 below.

[0019] [ka]

[0020] The sulfur-containing amine compound may be represented by the following Formula 6.

[0021] [ka]

[0022] In the above chemical formula 6, L 4 represents a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, R 10 is a sulfonamide group, a sulfonate group, a sulfone group, a sulfoxide group, a thiol group, a thiolate group, a thioester group, a thioether group, a thioamide group, a substituted or unsubstituted sulfur-containing heterocycloalkyl group having 3 to 10 carbon atoms, or a substituted or unsubstituted sulfur-containing heteroaryl group having 2 to 30 carbon atoms.

[0023] The sulfur-containing amine compound may be at least one compound selected from the compounds listed in Group 2 below.

[0024] [ka]

[0025] The composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist may contain 50 to 99.99 mass % of the organic solvent and 0.01 to 50 mass % of the additive, based on the total mass of the composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist.

[0026] The metal compound that can be included in the metal-containing photoresist can include at least one of an organic oxy group-containing tin compound and an organic carbonyloxy group-containing tin compound.

[0027] The metal compound contained in the metal-containing photoresist may be at least one selected from the group consisting of compounds represented by the following Chemical Formula 7 and polymers of these compounds.

[0028] [ka]

[0029] In the above chemical formula 7, R 18 -L is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, and a -OR a is selected from At this time, L a is a single bond or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, R a is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, R 19 ~R 21each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, -OR b and -OC(=O)R c is selected from among R 19 ~R 21 At least one of each independently represents -OR b and -OC(=O)R c is selected from In this case, R b each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; R c are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof.

[0030] In another embodiment, a pattern forming method includes the steps of applying a metal-containing photoresist composition on a substrate, applying the above-mentioned metal-containing photoresist edge bead removal composition along an edge of the substrate, a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate, exposing the metal-containing photoresist film to light, and developing.

[0031] In still another embodiment, a method for forming a pattern includes applying a metal-containing photoresist composition onto a substrate, removing edge beads of the metal-containing photoresist, drying and heating to form a metal-containing photoresist film on the substrate, exposing the metal-containing photoresist film to light, and developing the metal-containing photoresist film using the developer composition.

[0032] In still another embodiment, a method of forming a pattern includes applying the above-described composition for removing edge beads of metal-containing photoresist along an edge of the substrate, drying and heating to form a metal-containing photoresist film on the substrate, exposing the metal-containing photoresist film to light, and developing using the above-described metal-containing photoresist developer composition. Effect of the Invention

[0033] The edge bead removal composition for metal-containing photoresist according to an embodiment can meet the demands of smaller feature processing and patterning by reducing metal-based contamination inherent in metal-containing photoresist and removing photoresist applied to the edge and backside of a substrate.

[0034] The metal-containing photoresist developer composition according to another embodiment minimizes defects present in a metal-containing photoresist film after an exposure process, making it easy to develop, thereby enabling excellent contrast characteristics, excellent sensitivity, and reduced line edge roughness (LER). [Brief description of the drawings]

[0035] [Figure 1] 1 is a schematic diagram showing a photoresist coating apparatus according to an embodiment; [Diagram 2] 1A to 1C are schematic cross-sectional views showing a process sequence for explaining a pattern forming method. [Diagram 3]1A to 1C are schematic cross-sectional views showing a process sequence for explaining a pattern forming method. [Figure 4] 1A to 1C are schematic cross-sectional views showing a process sequence for explaining a pattern forming method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0036] Hereinafter, the embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, in describing the present invention, descriptions of already known functions or configurations will be omitted in order to clarify the gist of the present invention.

[0037] In order to clearly explain the present invention, parts that are not related to the description will be omitted, and the same or similar components will be given the same reference numerals throughout the specification. In addition, the size and thickness of each component shown in the drawings are arbitrarily shown for the convenience of explanation, and the present invention is not necessarily limited to those shown in the drawings.

[0038] In the drawings, the thickness of a plurality of layers and regions is exaggerated to clearly show the layers and regions. Also, for the convenience of explanation from the drawings, the thickness of some layers and regions is exaggerated. When a part such as a layer, film, region, plate, etc. is "on" or "on" another part, this includes not only the case where it is "directly on" the other part, but also the case where there is another part therebetween.

[0039] In this specification, "substituted" means that a hydrogen atom is substituted with a deuterium atom, a halogen group, a hydroxyl group, an amino group, a substituted or unsubstituted amino group having 1 to 30 carbon atoms, a nitro group, a substituted or unsubstituted silyl group having 1 to 40 carbon atoms, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a cyano group. "Unsubstituted" means that a hydrogen atom is not substituted with another substituent and remains a hydrogen atom.

[0040] In this specification, unless otherwise specified, the term "alkyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double bonds or triple bonds.

[0041] The alkyl group may be an alkyl group having 1 to 20 carbon atoms. More specifically, the alkyl group may be an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 6 carbon atoms. For example, an alkyl group having 1 to 5 carbon atoms means that the alkyl chain contains 1 to 5 carbon atoms and may be selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and t-butyl.

[0042] Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, and a hexyl group.

[0043] In this specification, unless otherwise defined, the term "cycloalkyl group" means an alicyclic hydrocarbon group, and includes, for example, a monovalent alicyclic hydrocarbon group.

[0044] Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0045] As used herein, unless otherwise defined, a "heterocycloalkyl group" means that the cycloalkyl group contains at least one heteroatom selected from the group consisting of N, O, S, P, and Si.

[0046] In this specification, unless otherwise defined, the term "alkenyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group and an aliphatic unsaturated alkenyl group containing one or more double bonds.

[0047] As used herein, unless otherwise defined, the term "alkynyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group and an aliphatic unsaturated alkynyl group containing one or more triple bonds.

[0048] As used herein, an "aryl group" refers to a cyclic substituent in which all elements of the substituent have p-orbitals and these p-orbitals form conjugation, and includes monocyclic or fused polycyclic (i.e., rings which share adjacent pairs of carbon atoms) functional groups.

[0049] In this specification, the term "heteroaryl group" means an aryl group containing at least one heteroatom selected from the group consisting of N, O, S, P and Si. Two or more heteroaryl groups can be directly linked through a sigma bond, or when the heteroaryl group contains two or more rings, the two or more rings can be fused to each other. When the heteroaryl group is a fused ring, each ring can contain 1 to 3 of the above heteroatoms.

[0050] More specifically, the substituted or unsubstituted aryl group having 6 to 30 carbon atoms may be, but is not limited to, 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 naphthacenyl 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 chrysenyl group, a substituted or unsubstituted benzophenanthrenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, or a combination thereof.

[0051] More specifically, the substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms is a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl 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 pyridyl 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 benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted phenyl ... or an unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzothiazinyl group, a substituted or unsubstituted acriridinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted benzonaphthofuranyl group, a substituted or unsubstituted benzonaphthothiophenyl group, a substituted or unsubstituted benzofuranofluorenyl group, a substituted or unsubstituted benzothiophenefluorenyl group, or a combination thereof, but is not limited to these.

[0052] FIG. 1 is a schematic diagram showing a photoresist coating apparatus according to an embodiment.

[0053] Referring to FIG. 1, a substrate support 1 on which a substrate (W) is placed is provided, and the substrate support 1 includes a spin chuck or a spin coater.

[0054] The substrate support 1 rotates in a first direction at a predetermined rotation speed to provide centrifugal force to the substrate (W). A spray nozzle 2 is located on the substrate support 1, and the spray nozzle 2 is located in a standby area away from the top of the substrate (W) and can move to the top of the substrate in the solution supply step to spray the photoresist solution 10. Thus, the photoresist solution 10 is applied to the surface of the substrate by the centrifugal force. At this time, the photoresist solution 10 supplied to the center of the substrate (W) is applied while spreading to the edge of the substrate (W) by the centrifugal force, and a part of it moves to the side of the substrate and the underside of the edge of the substrate.

[0055] That is, in the coating process, the photoresist solution 10 is mainly coated by a spin coating method, in which a predetermined amount of viscous photoresist solution 10 is supplied to the center of the substrate (W) and gradually spreads toward the edge of the substrate by centrifugal force.

[0056] Therefore, the thickness of the photoresist is formed evenly depending on the rotation speed of the substrate support.

[0057] However, as the solvent evaporates, the viscosity increases and the surface tension causes a relatively large amount of photoresist to accumulate at the edge of the substrate. Even more seriously, the photoresist accumulates on the underside of the edge of the substrate, which is called an edge bead 12.

[0058] Hereinafter, a composition for removing edge beads of a metal-containing photoresist or a developer composition for a metal-containing photoresist according to an embodiment will be described.

[0059] The composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist according to one embodiment of the present invention is substantially water-free and contains at least one additive selected from an amino acid-based compound, a sulfur-containing acid compound, and a sulfur-containing amine-based compound, and an organic solvent.

[0060] The amino acid-based compound has both an amino group and a carboxy group in the molecule, and thus has an improved binding strength with the photoresist. By applying a composition containing the amino acid-based compound, photoresist containing metal can be effectively removed.

[0061] The sulfur-containing acid compounds and sulfur-containing amine compounds contain "sulfur" to improve their binding strength with photoresist, and by applying a composition containing the same, photoresist containing metal can be effectively removed.

[0062] Meanwhile, in the above-mentioned composition for removing edge beads of metal-containing photoresist or developer composition for metal-containing photoresist, "substantially free of water" means that water is not selectively used as a component in the composition, and water of 1,000 ppm or less may be contained due to other impurities or external factors.

[0063] If the water content in the composition exceeds 1,000 ppm, there is a risk that the film will deteriorate due to hydration at the contact area with the photoresist.

[0064] For example, the amino acid compound is at least one of the compounds represented by the following chemical formulas 1 to 3.

[0065] [ka]

[0066] In the above Chemical Formula 1 to Chemical Formula 3, L 1 each independently represents a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, X 1 are each independently a single bond, O, S, or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, R is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; R 1 ~R 7 each independently represents a hydrogen atom, a hydroxy group, a mercapto group, an amino group, an amido group, a guanidino group, a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, n is an integer of 0 or 1.

[0067] For example, the above R 1 may be a hydrogen atom, a hydroxy group, a mercapto group, an amino group, an amido group, a guanidino group, a carboxyl group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted indolyl group, or a substituted or unsubstituted imidazole group.

[0068] For example, the above R 2 ~R 7 may each independently be a hydrogen atom, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted isobutyl group, or a substituted or unsubstituted sec-butyl group.

[0069] In this specification, the amino acid compound includes not only amino acids but also compounds derived from amino acids.

[0070] For example, the amino acid compound may be at least one of alanine, glycine, valine, leucine, isoleucine, proline, methionine, phenylalanine, tyrosine, tryptophan, serine, threonine, cysteine, asparagine, glutamine, aspartic acid, glutamic acid, histidine, lysine, arginine, and N-methylcysteine.

[0071] The sulfur-containing acid compound may be at least one of compounds represented by the following Formula 4 and Formula 5.

[0072] [ka]

[0073] In the above Chemical Formula 4 and Chemical Formula 5, L 2 and L 3 each independently represents a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, R 8 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, R 9 is a sulfur-containing substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a sulfur-containing substituted or unsubstituted heterocycloalkyl group having 3 to 10 carbon atoms, a sulfur-containing substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a sulfur-containing substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

[0074] In this specification, the term "sulfur-containing" includes all of the forms substituted with a sulfur-containing group and the forms containing sulfur in a heterocycle.

[0075] For example, the above R 8 can be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted isobutyl group, or a substituted or unsubstituted sec-butyl group.

[0076] For example, the above R 9may be a substituted or unsubstituted 1,3-dithiolane, a substituted or unsubstituted thiophene, a thiol group, a substituted or unsubstituted alkylthiol having 1 to 10 carbon atoms, or a substituted or unsubstituted arylthiol having 6 to 12 carbon atoms.

[0077] For example, the sulfur-containing acid compound is at least one selected from the compounds listed in Group 1 below.

[0078] [ka]

[0079] The sulfur-containing amine compound may be represented by the following formula 6:

[0080] [ka]

[0081] In the above chemical formula 6, L 4 represents a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, R 10 is a sulfonamide group, a sulfonate group, a sulfone group, a sulfoxide group, a thiol group, a thiolate group, a thioester group, a thioether group, a thioamide group, a substituted or unsubstituted sulfur-containing heterocycloalkyl group having 3 to 10 carbon atoms, or a substituted or unsubstituted sulfur-containing heteroaryl group having 2 to 30 carbon atoms.

[0082] For example, the sulfur-containing amine compound is at least one selected from the compounds listed in Group 2 below.

[0083] [ka]

[0084] In one embodiment, the composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist is substantially water-free and may contain 0.01 to 50 mass % of the additives described above and 50 to 99.99 mass % of an organic solvent, based on the total mass of the composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist.

[0085] In a specific embodiment, the composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist may contain the above-mentioned additive in an amount of 0.05 to 40 mass %, specifically 0.5 to 30 mass %, and more specifically 1 to 20 mass %, based on the total mass of the composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist.

[0086] Examples of organic solvents contained in the composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist according to a specific embodiment 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, isobutyl alcohol, hexanol, ethylene glycol, propylene glycol, heptanone, propylene carbonate, carbonate Butylene, 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), gamma-butyrolactone (GBL), 1-butanol, ethyl lactate (EL), diisopropyl ether (DIAE), acetylacetone, butyl lactate (n-Butyl lactate), 4-methyl-2-pentanol (or methyl isobutyl carbinol (MIBC)), 1-methoxy-2-propanol, 1-ethoxy-2-propanol, toluene, cyclopentanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, butyl acetate, methyl-2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate, or mixtures thereof.

[0087] The metal-containing photoresist edge bead removal compositions of the present invention are particularly effective in removing metal-containing photoresists, and more specifically, undesirable metal residues, such as tin-based metal residues.

[0088] In addition, the developer composition for metal-containing photoresist according to the present invention minimizes defects present in the metal-containing photoresist film after the exposure process and facilitates development, thereby achieving excellent pattern characteristics.

[0089] Also, excellent sensitivity and reduced line edge roughness (LER) can be achieved.

[0090] When other additives described later are contained, the organic solvent may be contained in the remaining amount excluding the contained components.

[0091] The composition for removing edge bead of a metal-containing photoresist or the developer composition for a metal-containing photoresist may further include at least one other additive selected from a surfactant, a dispersant, a moisture absorbent, and a coupling agent.

[0092] The surfactant may play a role in improving the coating uniformity of the composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist and improving the wetting. In an exemplary embodiment, the surfactant may be, but is not limited to, a sulfate salt, a sulfonate salt, a phosphate salt, a soap, an amine salt, a quaternary ammonium salt, a polyethylene glycol, an alkylphenol ethylene oxide adduct, a polyhydric alcohol, a nitrogen-containing vinyl polymer, or a combination thereof. For example, the surfactant may include an alkylbenzene sulfonate salt, an alkylpyridinium salt, a polyethylene glycol, or a quaternary ammonium salt. When the composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist includes the surfactant, the surfactant is included in an amount of 0.001% by weight to 3% by weight based on the total weight of the composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist.

[0093] The dispersant can serve to uniformly disperse each component of the metal-containing photoresist edge bead removal composition or the metal-containing photoresist developer composition in the photoresist composition. In an exemplary embodiment, the dispersant is an epoxy resin, polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, glucose, sodium dodecyl sulfate, sodium citrate, oleic acid, linoleic acid, or a combination thereof, but is not limited thereto. When the photoresist composition includes the dispersant, the dispersant is included in an amount of 0.001% to 5% by weight based on the total weight of the photoresist composition.

[0094] The moisture absorbent can prevent adverse effects of moisture in the metal-containing photoresist edge bead removal composition or metal-containing photoresist developer composition. For example, the moisture absorbent can prevent the metal contained in the metal-containing photoresist edge bead removal composition or metal-containing photoresist developer composition from being oxidized by moisture. In an exemplary embodiment, the moisture absorbent is polyoxyethylenenonylphenolether, polyethylene glycol, polypropylene glycol, polyacrylamide, or a combination thereof, but is not limited thereto. When the photoresist composition includes the moisture absorbent, the moisture absorbent is included in an amount of 0.001% to 10% by weight based on the total weight of the photoresist composition.

[0095] The coupling agent may play a role in improving adhesion to the lower layer when the composition for removing edge beads of the metal-containing photoresist or the developer composition for the metal-containing photoresist is coated on the lower layer. In an exemplary embodiment, the coupling agent may include a silane coupling agent. The silane coupling agent may be, but is not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, or trimethoxy[3-(phenylamino)propyl]silane. When the composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist contains the coupling agent, the coupling agent is contained in an amount of 0.001% by mass to 5% by mass based on the total mass of the composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist.

[0096] The metal compound contained in the metal-containing photoresist can include at least one of an organic oxy group-containing tin compound and an organic carbonyloxy group-containing tin compound.

[0097] For example, the metal compound contained in the metal-containing photoresist is at least one selected from the group consisting of compounds represented by the following chemical formula 7 and polymers of these compounds.

[0098] [ka]

[0099] In the above chemical formula 7, R 18 -L is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, and a -OR a is selected from At this time, L a is a single bond or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, R a is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, R 19 ~R 21 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, -OR b and -OC(=O)R cis selected from among R 19 ~R 21 At least one of each independently represents -OR b and -OC(=O)R c is selected from In this case, R b each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; R c are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof.

[0100] The metal compound contained in the metal-containing photoresist can be at least one of an organic oxy group-containing tin compound and an organic carbonyloxy group-containing tin compound.

[0101] For example, the metal compound that can be contained in the metal-containing photoresist can be at least one of an alkyloxy group-containing tin compound and an alkylcarbonyloxy group-containing tin compound.

[0102] Meanwhile, according to another embodiment, a method for forming a pattern may be provided, which includes removing edge beads using the above-mentioned composition for removing edge beads of a metal-containing photoresist. For example, the manufactured pattern may be a photoresist pattern. More specifically, it may be a negative type photoresist pattern or a positive type photoresist pattern. The formation of a negative type photoresist pattern will be described below as an example.

[0103] In one embodiment, a pattern formation method includes the steps of applying a metal-containing photoresist composition onto a substrate, applying the above-mentioned metal-containing photoresist edge bead removal composition along an edge of the substrate, a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate, exposing the metal-containing photoresist film to light, and developing.

[0104] More specifically, the step of forming a pattern using the metal-containing photoresist composition may include a step of applying the metal-containing photoresist composition onto a substrate on which a thin film has been formed by spin coating, slit coating, inkjet printing, etc., and drying the applied metal-containing photoresist composition to form a photoresist film. The metal-containing photoresist composition may include a tin-based compound, and for example, the tin-based compound may include at least one of an organic oxy group-containing tin compound and an organic carbonyloxy group-containing tin compound.

[0105] More specifically, the method may include applying an appropriate amount of the above-described composition for removing edge beads of metal-containing photoresist along the edge of the substrate while rotating the substrate at an appropriate speed (e.g., 500 rpm or more).

[0106] Next, a first heat treatment step is performed to heat the substrate on which the photoresist film is formed. The first heat treatment step can be performed at a temperature of 80° C. to 120° C., during which the solvent is evaporated and the photoresist film can be more firmly attached to the substrate.

[0107] Thereafter, the photoresist film is selectively exposed to light.

[0108] For example, examples of light that can be used in the above exposure process include light having wavelengths such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), as well as light having wavelengths corresponding to high energy such as EUV (Extreme Ultra Violet; wavelength 13.5 nm) and E-Beam (electron beam).

[0109] More specifically, the exposure light in one embodiment may be short-wavelength light having a wavelength range of 5 nm to 150 nm, or may be light having a wavelength corresponding to high energy such as EUV (wavelength 13.5 nm) or E-Beam (electron beam).

[0110] In the step of forming the photoresist pattern, a negative pattern may be formed.

[0111] The exposed areas of the photoresist film form polymers through crosslinking reactions such as condensation between organometallic compounds, and thus have different solubilities from the unexposed areas of the photoresist film.

[0112] Next, a second heat treatment step is performed on the substrate. The second heat treatment step can be performed at a temperature of 90° C. to 200° C. By performing the second heat treatment step, the exposed area of ​​the photoresist film becomes difficult to dissolve in a developer.

[0113] Specifically, the photoresist film corresponding to the unexposed region is dissolved using an organic solvent such as 2-heptanone and then removed, completing a photoresist pattern corresponding to the negative tone image.

[0114] The developer used in the pattern formation method according to one embodiment may be an organic solvent, for example, ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, etc.; alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, methanol, etc.; esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, γ-butyrolactone, etc.; aromatic compounds such as benzene, xylene, toluene, etc., or combinations thereof.

[0115] As described above, the photoresist pattern formed by exposure to light having a wavelength such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and high-energy light such as EUV (wavelength 13.5 nm) and E-Beam (electron beam) can have a thickness of 5 nm to 100 nm. For example, the photoresist pattern can be formed with a thickness of 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, or 5 nm to 20 nm.

[0116] Meanwhile, the photoresist pattern can have a half pitch of 50 nm or less, such as 40 nm or less, such as 30 nm or less, such as 20 nm or less, such as 15 nm or less, and a line width roughness of 10 nm or less, 5 nm or less, 3 nm or less, 2 nm or less.

[0117] According to another embodiment, a method for forming a pattern includes applying a metal-containing photoresist composition onto a substrate, removing edge beads of the metal-containing photoresist, drying and heating to form a metal-containing photoresist film on the substrate, exposing the metal-containing photoresist film to light, and developing the metal-containing photoresist film using the developer composition described above.

[0118] The step of applying a metal-containing photoresist composition onto a substrate is similar to that described above.

[0119] The edge bead removal step of the metal-containing photoresist can be carried out by applying an appropriate amount of a commonly known edge bead removal organic solvent or composition along the edge of the substrate while rotating the substrate at an appropriate speed (e.g., 500 rpm or greater).

[0120] The heat treatment steps of drying and heating to form a metal-containing photoresist film on the substrate are similar to those described above.

[0121] The step of exposing the metal-containing photoresist film is similar to that described above.

[0122] The photoresist film corresponding to the unexposed area is dissolved and then removed using the developer composition for the metal-containing photoresist, thereby completing the photoresist pattern corresponding to the negative tone image.

[0123] The method of forming a pattern by development will be specifically described below with reference to the drawings.

[0124] 2 to 4 are cross-sectional views showing the process steps for explaining the pattern formation method.

[0125] Referring to FIG. 2, the exposed photoresist film is developed to form a photoresist pattern 130P.

[0126] In an exemplary embodiment, the exposed photoresist film may be developed to remove unexposed areas of the photoresist film to form a photoresist pattern 130P consisting of exposed areas of the photoresist film. The photoresist pattern 130P may include a plurality of openings OP.

[0127] In an exemplary embodiment, the photoresist film may be developed using a negative-tone development (NTD) process, in which a metal-containing photoresist developer composition according to an embodiment may be used as a developer composition.

[0128] Referring to FIG. 3, the feature layer 110 is processed using the photoresist pattern 130P in the result of FIG.

[0129] For example, in order to process the feature layer 110, various processes may be performed, such as a process of etching the feature layer 110 exposed through the openings (OP) of the photoresist pattern 130P, a process of implanting impurity ions into the feature layer 110, a process of forming an additional film on the feature layer 110 through the openings (OP), a process of deforming a part of the feature layer 110 through the openings (OP), etc. Fig. 3 illustrates, as an example process for processing the feature layer 110, etching the feature layer 110 exposed through the openings (OP) to form a feature pattern 110P.

[0130] 4, the photoresist pattern 130P remaining on the feature pattern 110P is removed from the resultant structure of FIG 3. An ashing and stripping process can be used to remove the photoresist pattern 130P.

[0131] In yet another embodiment, a method for forming a pattern includes the steps of applying a metal-containing photoresist composition onto a substrate, applying the above-mentioned composition for removing edge beads of metal-containing photoresist along an edge of the substrate, a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate, exposing the metal-containing photoresist film to light, and developing using the above-mentioned metal-containing photoresist developer composition.

[0132] The specific method for each step is the same as described above. By simultaneously using the composition for removing edge beads of metal-containing photoresist or the developer composition for metal-containing photoresist according to the present invention in the edge bead removal step and the development step, the edge bead removal effect and the solubility of unexposed areas can be effectively improved, and the requirements for processing and patterning of smaller features can be met, and excellent contrast characteristics, excellent sensitivity, and reduced line edge roughness (LER) can be achieved. EXAMPLES

[0133] The present invention will be described in more detail with reference to examples of the preparation of the above-mentioned composition for removing edge beads of metal-containing photoresist and the developer composition for metal-containing photoresist. However, the technical features of the present invention are not limited to the following examples.

[0134] [Preparation of edge bead removal composition / developer composition for metal-containing photoresists] Example 1 Cysteine ​​was mixed with a solvent of propylene glycol methyl ether acetate (PGMEA) and ethyl lactate (EL) in a mass ratio of 9:1 in the composition ratio shown in Table 1, and then completely dissolved by shaking at room temperature (25°C).The mixture was then passed through a PTFE filter having a pore size of 1 μm to obtain the final composition.

[0135] (Examples 2 to 4 and Comparative Examples 1 to 3) A composition was obtained in the same manner as in Example 1, except that the additives and composition ratios were changed to those shown in Table 1 below.

[0136] [Table 1]

[0137] [Preparation of organometallic photoresist composition] An organometallic compound having the structure of the following chemical formula C was dissolved in 4-methyl-2-pentanol to a concentration of 1 mass %, and then filtered through a 0.1 μm PTFE syringe filter to prepare a photoresist composition.

[0138] [ka]

[0139] [Evaluation 1: Evaluation of the thickness of the thin film (Strip test) and evaluation of the amount of residual Sn in the developed film] 1.0 mL of the organometallic compound-containing photoresist composition according to the above manufacturing example was poured onto a 6-inch silicon wafer, left to stand for 20 seconds, and then spin-coated at a speed of 800 rpm for 30 seconds. Then, heat-treated at 180° C. for 60 seconds to obtain a coating film, the thickness of which was measured by an ellipsometry method. 10 mL of edge bead removal compositions obtained from Examples 1 to 4 and Comparative Examples 1 to 3 were poured onto the wafer on which the coating film was formed along the edge, spin-coated for 5 seconds, and then dried by rotating at a speed of 1,500 rpm. Then, heat-treated at 150° C. for 60 seconds to obtain a film, the thickness of which was measured again by an ellipsometry method, and the change in thickness before and after the edge bead removal process was confirmed and evaluated according to the following criteria. An ICP-MS (inductively coupled plasma mass) analysis using a vapor phase decomposition method (VPD-ICP-MS) was performed to confirm the amount of Sn remaining, and the results are shown in Table 2 below: *If the residual thickness is less than 2 Å: ○, if it is 2 Å or more: ×.

[0140] [Table 2]

[0141] Referring to Table 2, it can be seen that the composition for removing edge beads of metal-containing photoresist according to the embodiment has a superior metal removal effect and may further promote the reduction of residual metal compared to the composition for removing edge beads of metal-containing photoresist according to the comparative example. It can also be seen that when the same compound and organic solvent are used as in Comparative Example 3, but water is included, the metal removal effect is relatively reduced.

[0142] [Rating 2: Contrast performance] The metal-containing photoresist (PR) composition prepared above was spin-coated on an 8-inch wafer at 1,500 rpm for 30 seconds, and then heat-treated at 130° C. for 60 seconds to prepare a coated wafer.

[0143] This was exposed to a dose of 10-100 mJ using a KrF scanner (ASML PAS5500 / 700D) in a rectangular pattern of 1.2 cm x 0.9 cm, then heat-treated at 170°C for 60 seconds, developed using developer compositions according to Examples 1-4 and Comparative Examples 1-3, respectively, and finally heat-treated at 180°C for 60 seconds to complete a patterned wafer. The thickness of each exposed portion of the patterned wafer was measured, and the contrast performance (γ(contrast)) and sensitivity (D0) were calculated from the obtained contrast curve, and the results are shown in Table 3 below.

[0144]

number

[0145] [Evaluation 3: Sensitivity and Line Edge Roughness (LER) Evaluation] For a linear array of 50 circular pads with a diameter of 500 μm, EUV light was projected onto the wafer using a Lawrence Berkeley National Laboratory Micro Exposure Tool (MET). Increasing amounts of EUV light for each pad were applied by adjusting the exposure time for each pad.

[0146] The photoresist and substrate were then post-exposure baked (PEB) on a hotplate at 160° C. for 120 seconds. The baked films were then immersed in the developer solutions according to Examples 1-4 and Comparative Examples 1-3 for 30 seconds each, and then washed in the same developer for an additional 15 seconds to form a negative tone image, i.e., remove the unexposed portions of the coating. A final hotplate bake at 150° C. for 2 minutes completed the process.

[0147] The thickness of the remaining photoresist on the exposed pad was measured using polarimetry. The remaining thickness was measured for each exposure dose and graphed as a function of exposure dose. Dg (energy level at which development is complete) was evaluated into two levels for each type of photoresist according to the following criteria, as shown in Table 3 below.

[0148] In addition, the line edge roughness (LER) of the formed lines confirmed from the FE-SEM images was measured, and the LER was evaluated into three levels according to the following criteria and shown in Table 3 below.

[0149] [sensitivity] -A: 16 mJ / cm 2 less than -B: 16mJ / cm 2 End Line Edge Roughness (LER) -○: 4nm or less -△: More than 4nm and less than 7nm -×: More than 7nm

[0150] [Table 3]

[0151] Referring to Table 3, it can be seen that the application of the metal-containing photoresist developer composition according to the embodiment shows superior contrast performance, superior sensitivity, and reduced line edge roughness compared to the application of the metal-containing photoresist developer composition according to the comparative example.

[0152] Although specific embodiments of the present invention have been described and illustrated above, the present invention is not limited to the described embodiments, and it is obvious to those skilled in the art that various modifications and variations are possible without departing from the spirit and scope of the present invention. Therefore, such modifications or variations should not be understood separately from the technical spirit or perspective of the present invention, and the modified embodiments should belong to the scope of the claims of the present invention. [Explanation of symbols]

[0153] 1. Substrate support; 2 injection nozzles, 10 Photoresist solution, 12 Edge Beads, 100 boards, OP opening, 110 feature layers, 110P feature pattern, 130P photoresist pattern.

Claims

1. A composition for removing edge beads of a metal-containing photoresist or a developer composition for a metal-containing photoresist, which is substantially free of water and contains at least one additive selected from an amino acid compound, a sulfur-containing acid compound, and a sulfur-containing amine compound, and an organic solvent.

2. 2. The composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist according to claim 1, having a water content of 1,000 ppm or less.

3. The composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist according to claim 1, wherein the amino acid compound is at least one of compounds represented by the following formulas 1 to 3: 【Chemistry 1】 In the above Chemical Formulas 1 to 3, L １ each independently represents a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, X １ are each independently a single bond, O, S, or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; R is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; R １ ~R ７ each independently represents a hydrogen atom, a hydroxy group, a mercapto group, an amino group, an amido group, a guanidino group, a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, n is an integer of 0 or 1.

4. The composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist according to claim 1, wherein the amino acid compound is at least one of alanine, glycine, valine, leucine, isoleucine, proline, methionine, phenylalanine, tyrosine, tryptophan, serine, threonine, cysteine, asparagine, glutamine, aspartic acid, glutamic acid, histidine, lysine, arginine, and N-methylcysteine.

5. The composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist according to claim 1, wherein the sulfur-containing acid compound is at least one of compounds represented by the following formulas 4 and 5: 【Chemistry 2】 In the above Chemical Formula 4 and Chemical Formula 5, L ２ and L ３ each independently represents a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, R ８ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, R ９ is a substituted or unsubstituted sulfur-containing alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted sulfur-containing heterocycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted sulfur-containing aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted sulfur-containing heteroaryl group having 2 to 30 carbon atoms.

6. The composition for removing edge beads of metal-containing photoresist or the developer composition for metal-containing photoresist according to claim 1, wherein the sulfur-containing acid compound is at least one selected from the compounds listed in Group 1 below. 【Chemistry 3】

7. 2. The composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist according to claim 1, wherein the sulfur-containing amine compound is a compound represented by the following formula 6: 【Chemistry 4】 In the above chemical formula 6, L ４ is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, R １０ is a sulfonamide group, a sulfonate group, a sulfone group, a sulfoxide group, a thiol group, a thiolate group, a thioester group, a thioether group, a thioamide group, a substituted or unsubstituted sulfur-containing heterocycloalkyl group having 3 to 10 carbon atoms, or a substituted or unsubstituted sulfur-containing heteroaryl group having 2 to 30 carbon atoms.

8. The composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist according to claim 1, wherein the sulfur-containing amine compound is at least one selected from the compounds listed in Group 2 below. 【Chemistry 5】

9. Based on the total weight of the metal-containing photoresist edge bead removal composition or metal-containing photoresist developer composition, 0.01 to 50% by weight of the additive, and The composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist according to claim 1, comprising 50 to 99.99% by mass of the organic solvent.

10. 2. The composition for removing edge beads of a metal-containing photoresist or the developer composition for a metal-containing photoresist according to claim 1, wherein the metal compound contained in the metal-containing photoresist includes at least one of an organic oxy group-containing tin compound and an organic carbonyloxy group-containing tin compound.

11. The metal compound contained in the metal-containing photoresist is at least one selected from the group consisting of compounds represented by the following chemical formula 7 and polymers of these compounds. 【Chemistry 6】 In the above chemical formula 7, R １８ -R is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, and -L ａ -O-R ａ is selected from At this time, L ａ is a single bond or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, R ａ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, R １９ ~R ２１ each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, -OR ｂ and -OC(=O)R ｃ is selected from among R １９ ~R ２１ At least one of each independently represents -OR ｂ and -OC(=O)R ｃ is selected from At this time, R ｂ each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; R ｃ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof.

12. applying a metal-containing photoresist composition onto a substrate; applying a metal-containing photoresist edge bead removal composition according to any one of claims 1 to 11 along an edge of the substrate; a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate; exposing the metal-containing photoresist film to light; and A patterning method comprising a development step.

13. applying a metal-containing photoresist composition onto a substrate; Edge bead removal step of metal-containing photoresist; a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate; exposing the metal-containing photoresist film to light; and A method for forming a pattern, comprising the step of developing a metal-containing photoresist using a developer composition according to any one of claims 1 to 11.

14. applying a metal-containing photoresist composition onto a substrate; applying a metal-containing photoresist edge bead removal composition according to any one of claims 1 to 11 along an edge of the substrate; a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate; exposing the metal-containing photoresist film to light; and A method for forming a pattern, comprising the step of developing a metal-containing photoresist using a developer composition according to any one of claims 1 to 11.

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