A composition for removing edge beads from metal-containing photoresists or a developer composition for metal-containing photoresists, and a pattern formation method 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 from metal-containing photoresists or a developer composition for metal-containing photoresists, and a pattern forming method using the same. [Background technology]

[0002] In recent years, the semiconductor industry has seen a continuous reduction in critical size, which has led to a demand for new types of high-performance photoresist materials and patterning methods to meet the requirements for processing and patterning increasingly smaller features.

[0003] Furthermore, with the dramatic development of the semiconductor industry in recent years, semiconductor devices are required to have superior operating speed and large storage capacity. To meet these demands, technologies for processes that improve the integration density, reliability, and response speed of semiconductor devices are being developed. In particular, it is important to precisely control / implant impurities into the working regions of a silicon substrate and connect these regions to directly form elements and ultra-high-density circuits, which can be achieved through the photolithography process. That is, it is becoming important to consider integrating the photolithography process, which involves coating a substrate with photoresist, selectively exposing it with 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, the photoresist is mainly applied onto the substrate while rotating the silicon substrate. However, in this process, the photoresist is also applied to the substrate edge and the back surface, which may cause pattern defects in subsequent semiconductor manufacturing processes such as etching and ion implantation. Therefore, a process of stripping and removing the photoresist applied to the edge and the back surface of the silicon substrate using a thinner composition, that is, an EBR (EDGE BEAD REMOVAL) process, is carried out. In the above EBR process, a composition that exhibits excellent solubility in the photoresist and can effectively remove the beads and photoresist remaining on the substrate without generating photoresist residues is required.

[0005] In addition, there is a need to develop a photoresist that can ensure excellent etching resistance and resolution in the photolithography process, and at the same time improve sensitivity and CD (critical dimension) uniformity and can improve LER (line edge roughness) characteristics, as well as a developer composition that can achieve this.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems 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 having excellent sensitivity and LER characteristics.

[0008] Furthermore, the present invention aims to provide a pattern-forming method utilizing the above-mentioned composition. [Means for solving the problem]

[0009] The metal-containing photoresist edge bead removal composition or metal-containing photoresist developer composition according to the present invention is substantially water-free and contains at least one additive selected from amino acid compounds, sulfur-containing acid compounds, and sulfur-containing amine compounds, as well as an organic solvent.

[0010] The water content of the above-mentioned composition for removing edge beads from metal-containing photoresists or the developing solution composition for metal-containing photoresists may be 1,000 ppm or less.

[0011] The above amino acid-based compound may be at least one of the compounds represented by the following chemical formulas 1 to 3.

[0012] [ka]

[0013] Of the above chemical formulas 1 to 3, L 1 Each of these is independently an alkylene group with 1 to 10 carbon atoms, either single-bonded, substituted, or unsubstituted, or an arylene group with 6 to 20 carbon atoms, X 1 Each of these is independently a single bond, O, S, or an 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 of these is independently a hydrogen atom, a hydroxyl group, a mercapto group, an amino group, an amide 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, either 0 or 1.

[0014] The above amino acid compounds 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 above sulfur-containing acid compound may be at least one of the compounds represented by the following chemical formulas 4 and 5.

[0016] [ka]

[0017] In the above chemical formulas 4 and 5, L 2 and L 3 Each of these is independently an alkylene group with 1 to 10 carbon atoms, either single-bonded, substituted, or unsubstituted, or an arylene group with 6 to 20 carbon atoms, R 8 These are substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, or substituted or unsubstituted heteroaryl groups 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 can be at least one compound selected from the compounds listed in Group 1 below.

[0019]

Chemical formula

[0020] The sulfur-containing amine compound can be represented by the following Chemical formula 6.

[0021]

Chemical formula

[0022] 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, a sulfone group, a sulfoxide group, a thiol group, a thiolate group, a thioester group, a thioether group, a thioamide group, a sulfur-containing substituted or unsubstituted heterocycloalkyl group having 3 to 10 carbon atoms, or a sulfur-containing substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

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

[0024]

Chemical formula

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

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

[0027] The metal compound contained in the above-mentioned 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 This includes substituted or unsubstituted alkyl groups with 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups with 3 to 20 carbon atoms, substituted or unsubstituted alkenyl groups with 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups with 2 to 20 carbon atoms, substituted or unsubstituted aryl groups with 6 to 30 carbon atoms, substituted or unsubstituted arylalkyl groups with 7 to 30 carbon atoms, and -L a -OR a Selected from, At this point, L a This is an alkylene group with 1 to 20 carbon atoms, either single-bonded or substituted or unsubstituted. R a These are substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms. R 19 ~R 21These are, independently, substituted or unsubstituted alkyl groups with 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups with 3 to 20 carbon atoms, substituted or unsubstituted alkenyl groups with 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups with 2 to 20 carbon atoms, substituted or unsubstituted aryl groups with 6 to 30 carbon atoms, substituted or unsubstituted arylalkyl groups with 7 to 30 carbon atoms, and -OR b and -OC(=O)R c Selected from among, R 19 ~R 21 At least one of them is independently -OR b and -OC(=O)R c Selected from, In this case, R b Each of these is independently 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 Each of these is 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] A pattern formation method according to another embodiment 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 the 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; and developing.

[0031] Another pattern formation method according to another embodiment includes the steps of: applying a metal-containing photoresist composition onto a substrate; removing edge beads from the 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; and developing the metal-containing photoresist using the above-described metal-containing photoresist developer composition.

[0032] Another pattern formation method according to another embodiment includes the steps of: applying the above-described metal-containing photoresist edge bead removal composition along the edge of the substrate; a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate; an exposure step of the metal-containing photoresist film; and a development step of using the above-described metal-containing photoresist developer composition. [Effects of the Invention]

[0033] One embodiment of the metal-containing photoresist edge bead removal composition reduces metal-based contamination inherent in the metal-containing photoresist and removes photoresist coated on the edges and back surface of the substrate, thereby meeting the requirements for processing and patterning even smaller features.

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

[0035] [Figure 1] This is a schematic diagram showing a photoresist coating apparatus according to one embodiment. [Figure 2] This is a schematic cross-sectional diagram showing the process sequence to explain the pattern formation method. [Figure 3]This is a schematic cross-sectional diagram showing the process sequence to explain the pattern formation method. [Figure 4] This is a schematic cross-sectional diagram showing the process sequence to explain the pattern formation method. [Modes for carrying out the invention]

[0036] The embodiments of the present invention will be described in detail below with reference to the attached drawings. However, in order to clarify the gist of the present invention, descriptions of functions or configurations that are already known will be omitted.

[0037] To clearly illustrate the present invention, irrelevant parts have been omitted, and the same or similar components are denoted by the same reference numerals throughout the specification. Furthermore, the dimensions and thicknesses of each component shown in the drawings are provided arbitrarily for illustrative purposes, and the present invention is not necessarily limited to those shown.

[0038] In the drawings, the thicknesses are shown enlarged to clearly represent multiple layers and regions. Additionally, for explanatory purposes, the thicknesses of some layers and regions are exaggerated in the drawings. When a layer, film, region, plate, or other part is "on top of" or "above" another part, this includes not only cases where it is "directly on top of" another part, but also cases where there are other parts in between.

[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, "alkyl group" means a linear or branched aliphatic hydrocarbon group unless otherwise defined. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0041] The alkyl group described above 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 can 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 groups mentioned above include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, and hexyl groups.

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

[0044] The above-mentioned cycloalkyl groups may include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups.

[0045] In this specification, unless otherwise defined, "heterocycloalkyl group" means a cycloalkyl group containing at least one heteroatom selected from the group consisting of N, O, S, P, and Si.

[0046] In this specification, "alkenyl group" means an aliphatic unsaturated alkenyl group, which is a linear or branched aliphatic hydrocarbon group containing one or more double bonds, unless otherwise defined.

[0047] In this specification, unless otherwise defined, "alkynyl group" means a linear or branched aliphatic hydrocarbon group containing one or more triple bonds, which is an aliphatic unsaturated alkynyl group.

[0048] In this specification, "aryl group" means a substituent in which all elements of the cyclic substituent have p-orbitals and these p-orbitals form a conjugation, and includes monocyclic or fused polycyclic (i.e., rings sharing adjacent pairs of carbon atoms) functional groups.

[0049] In this specification, "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 sigma bonds, or, when the heteroaryl group contains two or more rings, the two or more rings can be fused together. When the heteroaryl group is a fused ring, each ring may contain 1 to 3 of the heteroatoms.

[0050] More specifically, the substituted or unsubstituted aryl groups having 6 to 30 carbon atoms may be, but are not limited to, substituted or unsubstituted phenyl groups, substituted or unsubstituted naphthyl groups, substituted or unsubstituted anthracenyl groups, substituted or unsubstituted phenantrenyl groups, substituted or unsubstituted naphthacenyl groups, substituted or unsubstituted pyrenyl groups, substituted or unsubstituted biphenyl groups, substituted or unsubstituted p-terphenyl groups, substituted or unsubstituted m-terphenyl groups, substituted or unsubstituted o-terphenyl groups, substituted or unsubstituted chrysenyl groups, substituted or unsubstituted benzophenantrenyl groups, substituted or unsubstituted triphenylene groups, substituted or unsubstituted perilennyl groups, substituted or unsubstituted fluorenyl groups, substituted or unsubstituted indenyl groups, or combinations thereof.

[0051] More specifically, substituted or unsubstituted heterocyclic groups with 2 to 30 carbon atoms include substituted or unsubstituted furanyl groups, substituted or unsubstituted thiophenyl groups, substituted or unsubstituted pyrrolyl groups, substituted or unsubstituted pyrazolyl groups, substituted or unsubstituted imidazolyl groups, substituted or unsubstituted triazolyl groups, substituted or unsubstituted oxazolyl groups, substituted or unsubstituted thiazolyl groups, substituted or unsubstituted oxadiazolyl groups, substituted or unsubstituted thiadiazolyl groups, substituted or unsubstituted pyridyl groups, substituted or unsubstituted pyrimidinyl groups, substituted or unsubstituted pyrazinyl groups, substituted or unsubstituted triazinyl groups, substituted or unsubstituted benzofuranyl groups, substituted or unsubstituted benzothiophenyl groups, substituted or unsubstituted benzimidazolyl groups, substituted or unsubstituted indolyl groups, substituted or unsubstituted quinolinyl groups, and substituted or unsubstituted The group may be an unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthilidinyl group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzothiadinyl group, a substituted or unsubstituted acrylidinyl 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 benzofuranofurenyl group, a substituted or unsubstituted benzothiophenfluorenyl group, or a combination thereof, but is not limited to these.

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

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

[0054] The substrate support unit 1 rotates in a first direction at a predetermined rotational speed, providing centrifugal force to the substrate (W). An injection nozzle 2 is located on the substrate support unit 1, and the injection nozzle 2 is positioned in a standby area away from the top of the substrate (W). During the solution supply stage, it moves to the top of the substrate to spray the photoresist solution 10. As a result, the photoresist solution 10 is applied to the substrate surface 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 edges of the substrate (W) by the centrifugal force, and a portion of it moves to the side surface of the substrate and the underside of the edges of the substrate.

[0055] In other words, during the coating process, the photoresist solution 10 is mainly applied by a spin coating method, with a predetermined amount of viscous photoresist solution 10 supplied to the center of the substrate (W), and then gradually spreading toward the edges of the substrate by centrifugal force.

[0056] Therefore, the thickness of the photoresist is formed flat by the rotation speed of the substrate support.

[0057] However, as the solvent evaporates, the viscosity increases further, and due to the action of surface tension, a relatively large amount of photoresist accumulates at the edges of the substrate. Even more serious is the accumulation of photoresist up to the underside of the edges of the substrate, which is called an edge bead 12.

[0058] The following describes a composition for removing edge beads from a metal-containing photoresist or a developer composition for a metal-containing photoresist according to one embodiment.

[0059] A composition for removing edge beads from a metal-containing photoresist or a 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 amino acid compounds, sulfur-containing acid compounds, and sulfur-containing amine compounds, as well as an organic solvent.

[0060] The above-mentioned amino acid-based compounds, by containing both amino and carboxyl groups in their molecules, have improved binding strength with photoresists. By applying a composition containing these compounds, photoresists containing metals can be effectively removed.

[0061] The sulfur-containing acid compounds and sulfur-containing amine compounds described above have improved binding strength with photoresists due to the inclusion of "sulfur," and by applying compositions containing these compounds, photoresists containing metals can be effectively removed.

[0062] On the other hand, in the above-mentioned composition for removing edge beads from metal-containing photoresists or developer solution composition for metal-containing photoresists, the phrase "substantially water-free" means that water is not selectively used as an ingredient in the composition, but it may contain 1,000 ppm or less of water 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 may deteriorate due to hydration at the photoresist contact area.

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

[0065] [ka]

[0066] Of the above chemical formulas 1 to 3, L 1 Each of these is independently an alkylene group with 1 to 10 carbon atoms, either single-bonded, substituted, or unsubstituted, or an arylene group with 6 to 20 carbon atoms, X 1 Each of these is independently a single bond, O, S, or an 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 of these is independently a hydrogen atom, a hydroxyl group, a mercapto group, an amino group, an amide 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, either 0 or 1.

[0067] For example, the above R 1 This may be a hydrogen atom, a hydroxyl group, a mercapto group, an amino group, an amide 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 Each of these may 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, amino acid-based compounds include not only amino acids but also compounds derived from amino acids.

[0070] For example, the above 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 above sulfur-containing acid compound may be at least one of the compounds represented by the following chemical formulas 4 and 5.

[0072] [ka]

[0073] In the above chemical formulas 4 and 5, L 2 and L 3 Each of these is independently an alkylene group with 1 to 10 carbon atoms, either single-bonded, substituted, or unsubstituted, or an arylene group with 6 to 20 carbon atoms, R 8 These are substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, or substituted or unsubstituted heteroaryl groups having 2 to 30 carbon atoms. R 9 These are sulfur-containing substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, sulfur-containing substituted or unsubstituted heterocycloalkyl groups having 3 to 10 carbon atoms, sulfur-containing substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, or sulfur-containing substituted or unsubstituted heteroaryl groups having 2 to 30 carbon atoms.

[0074] In this specification, "sulfur-containing" can include all forms in which a sulfur-containing group is substituted or in which sulfur is contained within a heterocycle.

[0075] For example, the above R 8 This 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 9This may 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 above sulfur-containing acid compound is at least one selected from the compounds listed in Group 1 below.

[0078] [ka]

[0079] The above sulfur-containing amine compound may also be represented by the following chemical formula 6.

[0080] [ka]

[0081] In the above chemical formula 6, L 4 This is an alkylene group having 1 to 10 carbon atoms, either single-bonded, substituted, or unsubstituted, or an arylene group having 6 to 20 carbon atoms, either substituted or unsubstituted. R 10 These are sulfonamide groups, sulfonates, sulfonates, sulfoxide groups, thiols, thiolates, thioesters, thioethers, thioamides, sulfur-containing substituted or unsubstituted heterocycloalkyl groups having 3 to 10 carbon atoms, or sulfur-containing substituted or unsubstituted heteroaryl groups having 2 to 30 carbon atoms.

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

[0083] [ka]

[0084] In one embodiment, the metal-containing photoresist edge bead removal composition or the metal-containing photoresist developer composition is substantially water-free and may contain the above-mentioned additives in an amount of 0.01 to 50% by mass and an organic solvent in an amount of 50 to 99.99% by mass, based on the total mass of the metal-containing photoresist edge bead removal composition or the metal-containing photoresist developer composition.

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

[0086] Examples of organic solvents contained in a metal-containing photoresist edge bead removal composition or metal-containing photoresist developer composition 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, and carbonic acid. 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), γ-butyrolactone (GBL), 1-butanol, ethyl lactate (EL), diisopropyl ether (DIAE), acetylacetone, butyl lactate (n-Butyl Examples include, but are not limited to, lactate, 4-methyl-2-pentanol (or methyl isobutylcarbinol (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 composition according to the present invention is particularly effective in removing metal-containing photoresists, and more specifically, undesirable metal residues, such as tin-based metal residues.

[0088] Furthermore, the metal-containing photoresist developer composition according to the present invention minimizes defects present in the metal-containing photoresist film after the exposure process, making it easier to develop and thereby enabling the realization of excellent pattern characteristics.

[0089] Furthermore, it can achieve excellent sensitivity and reduced line edge roughness (LER).

[0090] If other additives described later are included, the above organic solvent may be included in the remaining amount after excluding the components that are included.

[0091] The composition for removing edge beads from metal-containing photoresists or the developer composition for metal-containing photoresists may further contain at least one other additive selected from surfactants, dispersants, hygroscopic agents, and coupling agents.

[0092] The surfactant described above can play a role in improving the coating uniformity and wetting properties of the metal-containing photoresist edge bead removal composition or the metal-containing photoresist developer composition. In exemplary embodiments, the surfactant consists of, but is not limited to, sulfate ester salts, sulfonates, phosphate esters, soaps, amine salts, quaternary ammonium salts, polyethylene glycol, alkylphenol ethylene oxide adducts, polyhydric alcohols, nitrogen-containing vinyl polymers, or combinations thereof. For example, the surfactant may include alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, or quaternary ammonium salts. When the metal-containing photoresist edge bead removal composition or the metal-containing photoresist developer composition contains the surfactant, the surfactant is included in an amount of 0.001% to 3% by mass based on the total mass of the metal-containing photoresist edge bead removal composition or the metal-containing photoresist developer composition.

[0093] The above-mentioned dispersant can serve to ensure that each component constituting the metal-containing photoresist edge bead removal composition or the metal-containing photoresist developer composition is uniformly dispersed within the photoresist composition. In exemplary embodiments, the dispersant consists of, but is not limited to, epoxy resin, polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, glycose, sodium dodecyl sulfate, sodium citrate, oleic acid, linoleic acid, or a combination thereof. If the photoresist composition contains the above-mentioned dispersant, the dispersant is included in an amount of 0.001% to 5% by mass based on the total mass of the photoresist composition.

[0094] The above-mentioned desiccant can play a role in preventing adverse effects of moisture in the metal-containing photoresist edge bead removal composition or the metal-containing photoresist developer composition. For example, the above-mentioned desiccant can play a role in preventing the metal contained in the metal-containing photoresist edge bead removal composition or the metal-containing photoresist developer composition from being oxidized by moisture. In exemplary embodiments, the above-mentioned desiccant consists of, but is not limited to, polyoxyethylene nonylphenol ether, polyethylene glycol, polypropylene glycol, polyacrylamide, or a combination thereof. When the above-mentioned photoresist composition contains the above-mentioned desiccant, the above-mentioned desiccant is included in an amount of 0.001% to 10% by mass based on the total mass of the above-mentioned photoresist composition.

[0095] The coupling agent can play a role in improving the adhesion between the metal-containing photoresist edge bead removal composition or the metal-containing photoresist developer composition and the underlying film when coating the underlying film with the metal-containing photoresist edge bead removal composition. In exemplary embodiments, the coupling agent may include a silane coupling agent. The silane coupling agent consists of, 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. If the above-mentioned composition for removing edge beads from metal-containing photoresists or developer solution composition for metal-containing photoresists contains the above-mentioned coupling agent, the coupling agent is included in an amount of 0.001% to 5% by mass based on the total mass of the above-mentioned composition for removing edge beads from metal-containing photoresists or developer solution composition for metal-containing photoresists.

[0096] The metal compound contained in the above-mentioned metal-containing photoresist may include at least one of the following: an organic oxy group-containing tin compound and an organic carbonyl oxy group-containing tin compound.

[0097] For example, the metal compound contained in the above-mentioned 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 This includes substituted or unsubstituted alkyl groups with 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups with 3 to 20 carbon atoms, substituted or unsubstituted alkenyl groups with 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups with 2 to 20 carbon atoms, substituted or unsubstituted aryl groups with 6 to 30 carbon atoms, substituted or unsubstituted arylalkyl groups with 7 to 30 carbon atoms, and -L a -OR a Selected from, At this point, L a This is an alkylene group with 1 to 20 carbon atoms, either single-bonded or substituted or unsubstituted. R a These are substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms. R 19 ~R 21 These are, independently, substituted or unsubstituted alkyl groups with 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups with 3 to 20 carbon atoms, substituted or unsubstituted alkenyl groups with 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups with 2 to 20 carbon atoms, substituted or unsubstituted aryl groups with 6 to 30 carbon atoms, substituted or unsubstituted arylalkyl groups with 7 to 30 carbon atoms, and -OR b and -OC(=O)R cSelected from among, R 19 ~R 21 At least one of them is independently -OR b and -OC(=O)R c Selected from, In this case, R b Each of these is independently 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 Each of these is 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 above-mentioned metal-containing photoresist may be at least one of the following: an organic oxy group-containing tin compound and an organic carbonyl oxy group-containing tin compound.

[0101] For example, the metal compound that can be included in the above-mentioned metal-containing photoresist may be at least one of alkyloxy group-containing tin compounds and alkylcarbonyloxy group-containing tin compounds.

[0102] On the other hand, according to other embodiments, a pattern forming method can be provided that includes the step of removing edge beads using the metal-containing photoresist edge bead removal composition described above. 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. Below, as an example, the formation of a negative-type photoresist pattern is described.

[0103] A pattern formation method according to one embodiment 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 the edge of the substrate; a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate; an exposure step of the metal-containing photoresist film; and a development step.

[0104] More specifically, the step of forming a pattern using a metal-containing photoresist composition may include the steps 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 contain a tin-based compound, for example, the tin-based compound may contain at least one of an organic oxy group-containing tin compound and an organic carbonyl oxy group-containing tin compound.

[0105] More specifically, the process may include a step of applying an appropriate amount of the metal-containing photoresist edge bead removal composition described above 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 in which the substrate on which the photoresist film is formed is heated. This 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 adhered to the substrate.

[0107] Subsequently, the above-mentioned photoresist film is selectively exposed.

[0108] For example, examples of light that can be used in the above exposure process include not only light with wavelengths such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), but also light with wavelengths corresponding to high energies such as EUV (Extreme Ultra Violet; wavelength 13.5 nm) and E-Beam (electron beam).

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

[0110] During the process of forming the above-mentioned photoresist pattern, a negative-type pattern can be formed.

[0111] In the photoresist film, the exposed regions form polymers through crosslinking reactions such as condensation between organometallic compounds, resulting in different solubility levels from the unexposed regions of the photoresist film.

[0112] Next, a second heat treatment step is performed on the substrate. This second heat treatment step can be carried out at a temperature of 90°C to 200°C. By performing this second heat treatment step, the exposed areas of the photoresist film become difficult to dissolve in the developer solution.

[0113] Specifically, this can be done by using an organic solvent such as 2-heptanone to dissolve the photoresist film corresponding to the unexposed region, and then removing it, thereby completing the 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, and examples include ketones such as methyl ethyl ketone, acetone, cyclohexanone, and 2-heptanone; alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, and methanol; esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, and γ-butyrolactone; aromatic compounds such as benzene, xylene, and toluene; or combinations thereof.

[0115] As described above, photoresist patterns formed by exposure with 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 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 above photoresist patterns can be formed with thicknesses 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, and 5 nm to 20 nm.

[0116] On the other hand, the above photoresist pattern may have a half-pitch of 50 nm or less, for example 40 nm or less, for example 30 nm or less, for example 20 nm or less, for example 15 nm or less, and a pitch having a line width roughness of 10 nm or less, 5 nm or less, 3 nm or less, or 2 nm or less.

[0117] Another embodiment of the pattern formation method includes the steps of applying a metal-containing photoresist composition onto a substrate, removing edge beads from the metal-containing photoresist, a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate, an exposure step of the metal-containing photoresist film, and developing using the metal-containing photoresist developer composition described above.

[0118] The step of applying the metal-containing photoresist composition onto the substrate is the same as described above.

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

[0120] The heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate is the same as described above.

[0121] The step of exposing the metal-containing photoresist film is the same as described above.

[0122] By using the metal-containing photoresist developer composition described above to dissolve the photoresist film in the unexposed areas and then removing it, the photoresist pattern in the negative tone image can be completed.

[0123] The following section provides a detailed explanation of how to develop and form patterns, using a diagram as an example.

[0124] Figures 2 to 4 are cross-sectional views showing the process sequence to illustrate the pattern formation method.

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

[0126] In an exemplary embodiment, an exposed photoresist film can be developed to remove unexposed regions of the photoresist film, thereby forming a photoresist pattern (130P) consisting of the exposed regions of the photoresist film. The photoresist pattern (130P) may include a plurality of apertures (OPs).

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

[0128] Referring to Figure 3, the feature layer 110 is processed using the photoresist pattern (130P) in the result from Figure 2.

[0129] For example, various processes can be performed to process the feature layer 110, such as etching the feature layer 110 exposed through the aperture (OP) of the photoresist pattern 130P, implanting impurity ions into the feature layer 110, forming an additional film on the feature layer 110 through the aperture (OP), and deforming a part of the feature layer 110 through the aperture (OP). Figure 3 illustrates an example of a process for processing the feature layer 110, which involves etching the feature layer 110 exposed through the aperture (OP) to form the feature pattern 110P.

[0130] Referring to Figure 4, the photoresist pattern 130P remaining on the feature pattern 110P is removed from the result in Figure 3. Ashing and stripping processes can be used to remove the photoresist pattern 130P.

[0131] Another pattern formation method according to another embodiment 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 the edge of the substrate; a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate; an exposure step of the metal-containing photoresist film; and a development step of using the above-mentioned metal-containing photoresist developer composition.

[0132] The specific methods for each stage are the same as described above. By simultaneously using the edge bead removal composition for metal-containing photoresist or the developer composition for metal-containing photoresist according to the present invention in the edge bead removal stage and the development stage, the edge bead removal effect and the solubility of unexposed areas can be effectively improved, meeting the requirements for processing and patterning smaller features, and enabling excellent contrast characteristics, superior sensitivity, and reduced line edge roughness (LER). [Examples]

[0133] The present invention will be described in more detail below through examples relating to the production of the metal-containing photoresist edge bead removal composition and the metal-containing photoresist developer composition described above. However, the technical features of the present invention are not limited by the following examples.

[0134] [Manufacturing of compositions for removing edge beads from metal-containing photoresists / developing solution compositions] (Example 1) Cysteine ​​was mixed with propylene glycol methyl ether acetate (PGMEA) and ethyl lactate (EL) as solvents in a mass ratio of 9:1, according to the composition ratios shown in Table 1. The mixture was then shaken at room temperature (25°C) to completely dissolve the cysteine. The mixture was then passed through a PTFE filter with a pore size of 1 μm to obtain the final composition.

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

[0136] [Table 1]

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

[0138] [ka]

[0139] [Evaluation 1: Evaluation of small film thickness (Striptest) and evaluation of developed Sn residue] 1.0 mL of the organometallic compound-containing photoresist composition according to the above manufacturing example was placed on a 6-inch silicon wafer, allowed to stand for 20 seconds, and then spin-coated at a speed of 800 rpm for 30 seconds. The thickness of the resulting coating film, obtained by heat treatment at 180°C for 60 seconds, was measured by ellipsometry. On the wafer with the formed coating film, 10 mL each of the edge bead removal compositions obtained from Examples 1 to 4 and Comparative Examples 1 to 3 was placed along the edge and spin-coated for 5 seconds, then dried by rotation at a speed of 1,500 rpm. The thickness of the resulting film, obtained by heat treatment at 150°C for 60 seconds, was remeasured by ellipsometry. The change in thickness before and after the edge bead removal process was confirmed and evaluated according to the following criteria. Inductively coupled plasma mass (ICP-MS) analysis (VPD-ICP-MS) using vapor phase decomposition was performed to confirm the amount of residual Sn, 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 confirmed that the metal-containing photoresist edge bead removal composition according to the examples has a superior metal removal effect compared to the metal-containing photoresist edge bead removal composition according to the comparative examples, and may further promote the reduction of residual metal. Furthermore, it can be confirmed that even when using the same compound and organic solvent as in Comparative Example 3, the metal removal effect is relatively reduced when water is included.

[0142] [Evaluation 2: Contrast Performance] The metal-containing photoresist (PR) composition produced as described above was spin-coated onto an 8-inch wafer at 1,500 rpm for 30 seconds, and then heat-treated at 130°C for 60 seconds to produce a coated wafer.

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

[0144]

number

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

[0146] Subsequently, the photoresist and substrate were exposed to exposure and baked (PEB) on a hot plate at 160°C for 120 seconds. The baked films were immersed in the developer solutions of Examples 1-4 and Comparative Examples 1-3 for 30 seconds each, and then washed for an additional 15 seconds with the same developer to form a negative tone image, i.e., remove the unexposed coating. Finally, the process was completed by baking on a hot plate at 150°C for 2 minutes.

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

[0148] Furthermore, after measuring the line edge roughness (LER) of the formed lines confirmed from the FE-SEM images, the line edge roughness was evaluated in three stages according to the following criteria and is shown in Table 3 below.

[0149] [sensitivity] -A: 16mJ / cm 2 less than -B: 16mJ / cm 2 That's all. [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 confirmed that when the metal-containing photoresist developer composition according to the examples is applied, it exhibits superior contrast performance, superior sensitivity, and reduced line edge roughness compared to when the metal-containing photoresist developer composition according to the comparative example is applied.

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

[0153] 1. Substrate support section, 2 spray 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 from a metal-containing photoresist or a developer composition for a metal-containing photoresist, comprising substantially no water and at least one additive selected from an amino acid compound, a sulfur-containing acid compound, and a sulfur-containing amine compound, as well as an organic solvent, wherein the metal compound contained in the metal-containing photoresist comprises at least one of an organic oxy group-containing tin compound and an organic carbonyl oxy group-containing tin compound.

2. The metal-containing photoresist edge bead removal composition or metal-containing photoresist developer composition according to claim 1, wherein the water content is 1,000 ppm or less.

3. The amino acid-based compound is at least one of the compounds represented by the following chemical formulas 1 to 3, as described in claim 1, for the edge bead removal composition for metal-containing photoresist or the developer composition for metal-containing photoresist: 【Chemistry 1】 Among the above chemical formulas 1 to 3, L １ Each of these is independently an alkylene group having 1 to 10 carbon atoms, which is single-bonded, substituted, or unsubstituted, or an arylene group having 6 to 20 carbon atoms, X １ Each of these independently represents the number of single bonds, O, S, or substituted or unsubstituted carbon atoms. These are alkylene groups numbered 1 to 10. 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 of these is independently a hydrogen atom, a hydroxyl group, a mercapto group, an amino group, an amide 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, either 0 or 1.

4. The composition for removing edge beads from a metal-containing photoresist or a developer 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 sulfur-containing acid compound is at least one of the compounds represented by the following chemical formulas 4 and 5, as described in claim 1, for the edge bead removal composition for metal-containing photoresist or the developer composition for metal-containing photoresist: 【Chemistry 2】 In the above chemical formulas 4 and 5, L ２ and L ３ Each of these is independently an alkylene group having 1 to 10 carbon atoms, which is single-bonded, substituted, or unsubstituted, or an arylene group having 6 to 20 carbon atoms, R ８ These are substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, or substituted or unsubstituted heteroaryl groups having 2 to 30 carbon atoms. R ９ These are sulfur-containing substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, sulfur-containing substituted or unsubstituted heterocycloalkyl groups having 3 to 10 carbon atoms, sulfur-containing substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, or sulfur-containing substituted or unsubstituted heteroaryl groups having 2 to 30 carbon atoms.

6. The sulfur-containing acid compound is at least one selected from the compounds listed in Group 1 below, as described in claim 1, for removing edge beads from metal-containing photoresists or for developing metal-containing photoresists. 【Transformation 3】

7. The sulfur-containing amine compound is a compound represented by the following chemical formula 6, as described in claim 1 for the edge bead removal composition for metal-containing photoresist or the developer composition for metal-containing photoresist: 【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 These are a sulfonamide group, a sulfonate, a sulfone group, a sulfoxide group, a thiol group, a thioate group, a thioester group, a thioether group, a thioamide group, a sulfur-containing substituted or unsubstituted heterocycloalkyl group having 3 to 10 carbon atoms, or a sulfur-containing substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

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

9. Based on the total mass of the edge bead removal composition for metal-containing photoresists or the developer composition for metal-containing photoresists, The aforementioned additives amount to 0.01 to 50% by mass, and The composition for removing edge beads from 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. 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, according to claim 1, for removing edge beads from a metal-containing photoresist or for developing a metal-containing photoresist: 【Transformation 6】 In the above chemical formula 7, R １８ This includes substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C7-C30 arylalkyl groups, and -L ａ -O-R ａ Selected from, At this time, L ａ This is a single-bonded, substituted, or unsubstituted alkylene group having 1 to 20 carbon atoms. R ａ These are substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms. R １９ ~R ２１ Each of these independently comprises 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 -OR ｂ and -OC(=O)R ｃ Selected from among, R １９ ~R ２１ At least one of them is independently -OR ｂ and -OC(=O)R ｃ Selected from, At this time, R ｂ Each of these is independently 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 Each of these is 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.

11. A step of applying a metal-containing photoresist composition onto a substrate; A step of applying the metal-containing photoresist edge bead removal composition according to any one of claims 1 to 10 along the edge of the substrate; A heat treatment step in which a metal-containing photoresist film is formed on the substrate by drying and heating; The step of exposing the metal-containing photoresist film; and A pattern formation method, including a development step.

12. A step of applying a metal-containing photoresist composition onto a substrate; Edge bead removal step in metal-containing photoresist; A heat treatment step in which a metal-containing photoresist film is formed on the substrate by drying and heating; The step of exposing the metal-containing photoresist film; and A method for forming a pattern, comprising the step of developing using a metal-containing photoresist developer composition according to any one of claims 1 to 10.

13. A step of applying a metal-containing photoresist composition onto a substrate; A step of applying the metal-containing photoresist edge bead removal composition according to any one of claims 1 to 10 along the edge of the substrate; A heat treatment step in which a metal-containing photoresist film is formed on the substrate by drying and heating; The step of exposing the metal-containing photoresist film; and A method for forming a pattern, comprising the step of developing using a metal-containing photoresist developer composition according to any one of claims 1 to 10.

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