Method of forming patterns

Abstract

To provide a method of forming patterns.SOLUTION: A method of forming patterns comprises the steps of coating a metal-containing resist composition on a substrate; coating a composition for removing edge beads along the edge of the substrate; drying and heating to form a metal-containing resist film on the substrate; and exposing and developing to form a resist pattern, wherein the composition for removing edge beads includes at least one additive selected from a phosphorous acid-based compound, a hypophosphorous acid-based compound, a sulfurous acid-based compound, and a hydroxamic acid-based compound, and an organic solvent.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present description relates to a patterning method that includes applying an edge bead removal composition to reduce metal contamination along the wafer edge. [Background technology]

[0002] Recently, the semiconductor industry has been experiencing a continuous reduction in critical dimensions, which has required new types of high performance photoresist materials and patterning methods to meet the demands of processing and patterning smaller and smaller features.

[0003] Furthermore, recent rapid developments in the semiconductor industry have led to demands for faster operating speeds and larger storage capacities for semiconductor devices, and process technologies are being developed to keep pace with these demands and improve the integration density, reliability, and response speed of semiconductor devices. It is particularly important to precisely control / inject impurities into active regions of silicon substrates so that these regions can be interconnected to form elements and ultra-high density integrated circuits, which can be achieved through photolithography. In other words, it has become important to consider the integration of the photolithography process, which involves 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, resist is typically applied to the substrate while the substrate is rotated. During this process, resist is also applied to the edge and backside of the substrate, which can cause compression or pattern defects in subsequent semiconductor processes such as etching and ion implantation. Therefore, a process of stripping and removing the photoresist applied to the edge and backside 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 the bead and photoresist remaining on the substrate without leaving any resist residue. Summary of the Invention [Problem to be solved by the invention]

[0005] One embodiment provides a method for forming a pattern, particularly a method for forming a pattern including the step of applying an edge bead removal composition. [Means for solving the problem]

[0006] According to one embodiment, a method for forming a pattern includes the steps of: applying a metal-containing resist composition on a substrate; applying an edge bead removal composition along an edge of the substrate; heat-treating the substrate by drying and heating to form a metal-containing resist film on the substrate; and exposing and developing the substrate to form a resist pattern. The edge bead removing composition may include at least one additive selected from the group consisting of a phosphorous acid compound, a hypophosphorous acid compound, a sulfurous acid compound, and a hydroxamic acid compound, and an organic solvent.

[0007] The edge bead removing composition may contain the additive in an amount of 0.01 to 50% by weight and the organic solvent in an amount of 50 to 99.99% by weight.

[0008] After the exposure and development steps, the method may further include applying a composition for removing edge bead.

[0009] The phosphorous acid compound may be at least one of phosphonic acid, methylphosphonic acid, ethylphosphonic acid, butylphosphonic acid, hexylphosphonic acid, n-octylphosphonic acid, tetradecylphosphonic acid, octadecylphosphonic acid, phenylphosphonic acid, vinylphosphonic acid, aminomethylphosphonic acid, methylenediaminetetramethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, 1-amino-1-phosphonooctylphosphonic acid, etidronic acid, 2-aminoethylphosphonic acid, 3-aminopropylphosphonic acid, 6-hydroxyhexylphosphonic acid, decylphosphonic acid, methylenediphosphonic acid, nitrilotrimethylenetriphosphonic acid, 1H,1H,2H,2H-perfluorooctanephosphonic acid, or a combination thereof.

[0010] The hypophosphorous acid compound may be at least one of phosphinic acid, phenylphosphinic acid, diphenylphosphinic acid, bis(4-methoxyphenyl)phosphinic acid, bis(hydroxymethyl)phosphinic acid, p-(3-aminopropyl)-p-butylphosphinic acid, or a combination thereof.

[0011] The hydroxamic acid compound may be at least one of formohydroxamic acid, acetohydroxamic acid, benzohydroxamic acid, salicylhydroxamic acid, 2-aminobenzohydroxamic acid, 2-chlorobenzohydroxamic acid, 2-fluorobenzohydroxamic acid, 2-nitrobenzohydroxamic acid, 3-nitrobenzohydroxamic acid, 4-aminobenzohydroxamic acid, 4-chlorobenzohydroxamic acid, 4-fluorobenzohydroxamic acid, 4-nitrobenzohydroxamic acid, or a combination thereof.

[0012] The edge bead removal composition may have a moisture content of 1,000 ppm or less.

[0013] The metal-containing resist composition may include a metal compound containing at least one of an alkyltin oxo group and an alkyltin carboxyl group.

[0014] The metal compound contained in the metal-containing resist can be represented by the following Chemical Formula 1.

[0015] [ka]

[0016] In the above Chemical Formula 1, R 1 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 or C30 arylalkyl group, and -R a -OR b (where R a is a substituted or unsubstituted C1-C20 alkylene group, and R b is a substituted or unsubstituted C1-C20 alkyl group; R 2 ~R 4 are each independently -OR c or -OC(=O)R d is selected from R c is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R dis hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof. [Effects of the Invention]

[0017] A patterning method according to one embodiment can meet the demands of smaller feature processing and patterning by reducing metal-based contamination inherent in metal-containing resist and removing resist applied to the edge and backside of the substrate. [Brief explanation of the drawings]

[0018] [Figure 1] FIG. 1 is a schematic diagram showing a photoresist coating apparatus. DETAILED DESCRIPTION OF THE INVENTION

[0019] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings, in which: In the description, descriptions of known functions or configurations will be omitted in order to clarify the gist of the description.

[0020] In order to clarify the present description, parts unnecessary for the description have been omitted, and the same or similar components have been designated by the same reference numerals throughout the specification. Furthermore, the size and thickness of each component shown in the drawings are arbitrarily shown for the convenience of description, and the present description is not necessarily limited to those shown in the drawings.

[0021] In the drawings, the thickness of multiple layers and regions is exaggerated to clearly show them. Also, in the drawings, the thickness of some layers and regions is exaggerated for the convenience of explanation. When a layer, film, region, plate, or other portion is said to be "on" another portion, this includes not only the case where it is "directly on" the other portion, but also the case where there is another portion therebetween.

[0022] FIG. 1 is a schematic diagram showing a photoresist coating apparatus.

[0023] 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.

[0024] The substrate support 1 rotates in a first direction at a predetermined rotational speed to apply centrifugal force to the substrate W. A spray nozzle 2 is located on the substrate support 1. The spray nozzle 2 is located in an atmospheric region away from the top of the substrate W and moves to the top of the substrate during the solution supply step to spray the photoresist solution 10. As a result, 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 spread to the periphery of the substrate W by the centrifugal force, and some of it moves to the side of the substrate and the underside of the periphery of the substrate.

[0025] That is, in the coating process, the photoresist solution 10 is mainly applied by spin coating, and a predetermined amount of viscous photoresist solution 10 is supplied to the center of the substrate W and gradually spreads toward the periphery of the substrate by centrifugal force.

[0026] Therefore, the thickness of the photoresist is formed evenly depending on the rotation speed of the substrate support.

[0027] However, as the solvent evaporates and the viscosity gradually increases, a relatively large amount of photoresist accumulates around the periphery of the substrate due to the action of surface tension. In the worst case, the photoresist accumulates all the way down to the periphery of the substrate, which is called an edge bead 12.

[0028] A pattern forming method according to one embodiment will be described below.

[0029] According to one embodiment, a method for forming a pattern includes applying a metal-containing resist composition onto a substrate, applying an edge bead removal composition along an edge of the substrate, performing a heat treatment by drying and heating to form a metal-containing resist film on the substrate, and then performing exposure and development to form a resist pattern.

[0030] More specifically, the step of forming a pattern using the metal-containing resist composition may include applying the metal-containing resist 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 resist composition to form a photoresist film. The metal-containing resist composition may include a tin-based compound, and for example, the tin-based compound may include at least one of an alkyltin oxo group and an alkyltin carboxyl group.

[0031] For example, the metal compound contained in the metal-containing resist may be represented by the following Chemical Formula 1:

[0032] [ka]

[0033] In the above Chemical Formula 1, R 1 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 or C30 arylalkyl group, and -R a -OR b (where R a is a substituted or unsubstituted C1-C20 alkylene group, and R b is a substituted or unsubstituted C1-C20 alkyl group; R 2 ~R 4are each independently -OR c or -OC(=O)R d is selected from R c is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R d is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.

[0034] In one embodiment, the edge bead removal composition may include at least one additive selected from the group consisting of a phosphorous acid-based compound, a hypophosphorous acid-based compound, a sulfurous acid-based compound, and a hydroxamic acid-based compound, and an organic solvent.

[0035] The edge bead removing composition may contain the additive in an amount of 0.01 to 50% by weight and the organic solvent in an amount of 50 to 99.99% by weight.

[0036] In one specific embodiment, the edge bead removing composition may contain the additive in an amount of 0.1 to 40 wt %, specifically 0.5 to 30 wt %, more specifically 1 to 20 wt %.

[0037] Examples of organic solvents that may be included in the edge bead removal composition according to one embodiment include propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), propylene glycol butyl ether (PGBE), ethylene glycol methyl ether, diethyl glycol ethyl methyl ether, dipropyl glycol dimethyl ether, ethanol, 2-butoxyethanol, n-propanol, isopropanol, n-butanol, isobutyl alcohol, hexanol, ethylene glycol, propylene glycol, heptanone, propylene carbonate, butylene carbonate, diethyl ether, dibutyl ether, ethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diisopentyl ether, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, acetonitrile, diacetone alcohol, 3,3-dimethyl-2-butanone, N-methyl-2-pyrrolidone, dimethylacetamide, cyclohexanone methyl-2-hydroxy-2-methylpropanoate (HBM), gamma-butyrolactone (GBL), 1-butanol (n-butanol), ethyl lactate (EL), dibutyl ether (DBE), diisopropyl ether (DIAE), acetylacetone, butyl lactate (n-butylactate), 4-methyl-2-pentanol (or methyl isobutyl carbinol (MIBC), 1-methoxy-2-propanol, 1-ethoxy-2-propanol, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, methyl 2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate, or mixtures thereof. ,

[0038] Edge bead removal compositions according to the present invention can be particularly effective in removing metal-containing resists, and more particularly, undesirable metal residues, such as tin-based metal residues.

[0039] For example, the phosphorous acid compound may be at least one of phosphonic acid, methylphosphonic acid, ethylphosphonic acid, butylphosphonic acid, hexylphosphonic acid, n-octylphosphonic acid, tetradecylphosphonic acid, octadecylphosphonic acid, phenylphosphonic acid, vinylphosphonic acid, aminomethylphosphonic acid, methylenediaminetetramethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, 1-amino-1-phosphonooctylphosphonic acid, etidronic acid, 2-aminoethylphosphonic acid, 3-aminopropylphosphonic acid, 6-hydroxyhexylphosphonic acid, decylphosphonic acid, methylenediphosphonic acid, nitrilotrimethylenetriphosphonic acid, 1H,1H,2H,2H-perfluorooctanephosphonic acid, or a combination thereof.

[0040] For example, the hypophosphorous acid compound can be at least one of phosphinic acid, phenylphosphinic acid, diphenylphosphinic acid, bis(4-methoxyphenyl)phosphinic acid, bis(hydroxymethyl)phosphinic acid, p-(3-aminopropyl)-p-butylphosphinic acid, or a combination thereof.

[0041] For example, the hydroxamic acid compound may be at least one of formohydroxamic acid, acetohydroxamic acid, benzohydroxamic acid, salicylhydroxamic acid, 2-aminobenzohydroxamic acid, 2-chlorobenzohydroxamic acid, 2-fluorobenzohydroxamic acid, 2-nitrobenzohydroxamic acid, 3-nitrobenzohydroxamic acid, 4-aminobenzohydroxamic acid, 4-chlorobenzohydroxamic acid, 4-fluorobenzohydroxamic acid, 4-nitrobenzohydroxamic acid, or a combination thereof.

[0042] The edge bead removing composition may contain at least one additive selected from the group consisting of hypophosphorous acid compounds, sulfurous acid compounds, and hydroxamic acid compounds, so that the moisture content in the composition may be 1,000 ppm or less.

[0043] If the water content in the composition exceeds 1,000 ppm, film deformation may occur due to hydration at the contact area with the photoresist.

[0044] For example, if phosphoric acid or the like is included as an additive, the moisture content may exceed 1,000 ppm, causing film deformation due to hydration at the contact point with the photoresist.

[0045] Specifically, the step of applying the edge bead removal composition may include applying an appropriate amount of the edge bead removal composition along the edge of the substrate while spinning the substrate at an appropriate speed (e.g., 500 rpm or more).

[0046] Next, a first heat treatment process is performed to heat the substrate on which the photoresist film is formed. The first heat treatment process can be performed at a temperature of about 80°C to about 120°C, during which the solvent evaporates and the photoresist film can be more firmly attached to the substrate.

[0047] Then, the photoresist film is selectively exposed to light.

[0048] Examples of light that can be used in the exposure process include light with short wavelengths such as activation radiation i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), as well as light with high energy wavelengths such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0049] 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 may be light having a high energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0050] In the step of forming the photoresist pattern, a negative type pattern may be formed.

[0051] The exposed area of ​​the photoresist film forms a polymer through a crosslinking reaction, such as condensation between organometallic compounds, and thus has a different solubility from the unexposed area of ​​the photoresist film.

[0052] Next, the substrate is subjected to a second heat treatment step, which can be performed at a temperature of about 90° C. to about 200° C. By performing the second heat treatment step, the exposed area of ​​the photoresist film becomes difficult to dissolve in a developer.

[0053] Specifically, the photoresist film corresponding to the unexposed area is dissolved using an organic solvent such as 2-heptanone and then removed, thereby completing the photoresist pattern corresponding to the negative tone image.

[0054] The developer used in the pattern formation method according to one embodiment may be an organic solvent, and examples thereof 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 methyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, and butyrolactone; aromatic compounds such as benzene, xylene, and toluene; and combinations thereof.

[0055] In addition, the pattern forming method may further include a step of applying an edge bead removal composition after the exposure and development processes. Specifically, the step of applying the edge bead removal composition may include applying an appropriate amount of the edge bead removal composition along the edge of the substrate while spinning the substrate at an appropriate speed (e.g., 500 rpm or more).

[0056] As described above, photoresist patterns formed by exposure to 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 (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam), can have a thickness of 5 nm to 100 nm. For example, the photoresist patterns can have 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, or 5 nm to 20 nm.

[0057] Meanwhile, the photoresist pattern may have a half-pitch of about 50 nm or less, e.g., 40 nm or less, e.g., 30 nm or less, e.g., 20 nm or less, e.g., 15 nm or less, and a pitch with a line width roughness of about 10 nm or less, about 5 nm or less, about 3 nm or less, or about 2 nm or less.

[0058] [Example] The present invention will be described in more detail below with reference to examples of preparing the edge bead removal composition described above, but the technical features of the present invention are not limited to the following examples.

[0059] Examples 1 to 5 and Comparative Examples 1 to 3: Preparation of edge bead removal composition The additives and solvents are mixed according to the compositions shown in Table 1 below, and then shaken at room temperature (25°C) to completely dissolve. The mixture is then passed through a PTFE filter with a pore size of 1 μm to obtain the final edge bead removal composition.

[0060] Preparation Example: Preparation of organometallic photoresist composition An organometallic compound having the following chemical formula C was dissolved in 4-methyl-2-pentanol to a concentration of 1 wt %, and then filtered through a 0.1 μm PTFE syringe filter to prepare a photoresist composition.

[0061] [ka]

[0062] Evaluation: Residual tin (Sn) content 1.0 mL of the organometallic photoresist composition according to the above Preparation Example was dispensed onto a 4-inch silicon wafer, left to stand for 20 seconds, and then spin-coated at 1,500 rpm for 30 seconds. While the wafer with the coating film formed thereon was rotated at 800 rpm, 6.5 mL of each of the edge bead removal compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 3 was dispensed along the edge, spin-coated for 3 seconds, and then dried for 25 seconds while rotating at 1,500 rpm. The process of dispensing the edge bead removal composition, spin-coating, and drying was repeated three times. The wafer was then baked at 150°C for 60 seconds, and the Sn content was confirmed through VPD ICP-MS analysis.

[0063] [Table 1]

[0064] Referring to Table 1, it can be seen that the edge bead removing compositions of Examples 1 to 5 have a superior metal removing effect compared to the edge bead removing compositions of Comparative Examples 1 to 3, and can further promote the reduction of residual metal.

[0065] Although specific embodiments of the present invention have been described and illustrated above, it will be apparent to those skilled in the art that the present invention is not limited to the described embodiments and that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modifications and variations should not be understood individually from the technical spirit and perspective of the present invention, and the modified embodiments should be considered to fall within the scope of the claims of the present invention.

[0066] [1] applying a metal-containing resist composition onto a substrate; applying an edge bead removal composition along an edge of the substrate; a heat treatment step of drying and heating to form a metal-containing resist film on the substrate; and A step of forming a resist pattern by exposure and development Including, The edge bead removing composition comprises at least one additive selected from the group consisting of a phosphorous acid compound, a hypophosphorous acid compound, a sulfurous acid compound, and a hydroxamic acid compound, and an organic solvent. [2] The pattern forming method according to [1], wherein the composition for removing an edge bead contains the additive in an amount of 0.01 to 50% by weight and the organic solvent in an amount of 50 to 99.99% by weight. [3] The pattern forming method according to [1], further comprising the step of applying an edge bead removal composition after the exposure and development steps. [4] The pattern formation method according to [1], wherein the phosphorous acid compound is at least one of phosphonic acid, methylphosphonic acid, ethylphosphonic acid, butylphosphonic acid, hexylphosphonic acid, n-octylphosphonic acid, tetradecylphosphonic acid, octadecylphosphonic acid, phenylphosphonic acid, vinylphosphonic acid, aminomethylphosphonic acid, methylenediaminetetramethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, 1-amino-1-phosphonooctylphosphonic acid, etidronic acid, 2-aminoethylphosphonic acid, 3-aminopropylphosphonic acid, 6-hydroxyhexylphosphonic acid, decylphosphonic acid, methylenediphosphonic acid, nitrilotrimethylenetriphosphonic acid, 1H,1H,2H,2H-perfluorooctanephosphonic acid, or a combination thereof. [5] The pattern formation method according to [1], wherein the hypophosphorous acid compound is at least one of diphenylphosphinic acid, bis(4-methoxyphenyl)phosphinic acid, phosphinic acid, bis(hydroxymethyl)phosphinic acid, phenylphosphinic acid, p-(3-aminopropyl)-p-butylphosphinic acid, and combinations thereof. [6] The pattern formation method according to [1], wherein the hydroxamic acid compound is at least one of formohydroxamic acid, acetohydroxamic acid, benzohydroxamic acid, salicylhydroxamic acid, 2-aminobenzohydroxamic acid, 2-chlorobenzohydroxamic acid, 2-fluorobenzohydroxamic acid, 2-nitrobenzohydroxamic acid, 3-nitrobenzohydroxamic acid, 4-aminobenzohydroxamic acid, 4-chlorobenzohydroxamic acid, 4-fluorobenzohydroxamic acid, 4-nitrobenzohydroxamic acid, and combinations thereof. [7] The pattern forming method according to [1], wherein the water content of the edge bead removing composition is 1,000 ppm or less. [8] The pattern formation method according to [1], wherein the metal-containing resist composition contains a metal compound containing at least one of an alkyltin oxo group and an alkyltin carboxyl group. [9] The pattern forming method according to [8], wherein the metal compound is represented by the following chemical formula 1: [ka] (In the above Chemical Formula 1, R 1 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 or C30 arylalkyl group, and -R a -OR b (where R a is a substituted or unsubstituted C1-C20 alkylene group, and R b is a substituted or unsubstituted C1-C20 alkyl group; R 2 ~R 4 are each independently -OR c or -OC(=O)R d is selected from R cis a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R d is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof. [Explanation of symbols]

[0067] 1: Substrate support part 2: Injection nozzle 10: Photoresist solution 12: Edge bead

Claims

1. 1. A composition for removing edge bead of a metal-containing resist, comprising: a phosphorous-based compound, which is at least one of methylphosphonic acid, ethylphosphonic acid, butylphosphonic acid, hexylphosphonic acid, n-octylphosphonic acid, tetradecylphosphonic acid, octadecylphosphonic acid, phenylphosphonic acid, vinylphosphonic acid, aminomethylphosphonic acid, methylenediaminetetramethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, 1-amino-1-phosphonooctylphosphonic acid, etidronic acid, 2-aminoethylphosphonic acid, 3-aminopropylphosphonic acid, 6-hydroxyhexylphosphonic acid, decylphosphonic acid, methylenediphosphonic acid, nitrilotrimethylenetriphosphonic acid, 1H,1H,2H,2H-perfluorooctanephosphonic acid, and a combination thereof; and an organic solvent; A composition for removing edge bead from a metal-containing resist, wherein the metal compound contained in the metal-containing resist contains at least one of an alkyltin oxo group and an alkyltin carboxyl group.

2. 2. The composition for removing edge bead of metal-containing resist according to claim 1, wherein the composition for removing edge bead contains the phosphorous-based compound in an amount of 0.01 to 50 wt % and the organic solvent in an amount of 50 to 99.99 wt %.

3. 2. The composition for removing edge bead of metal-containing resist according to claim 1, wherein the composition for removing edge bead contains the phosphorous compound in an amount of 0.1 to 40% by weight.

4. 2. The composition for removing edge bead of metal-containing resist according to claim 1, wherein the composition for removing edge bead contains the phosphorous compound in an amount of 0.5 to 30 wt %.

5. 2. The composition for removing edge bead of metal-containing resist according to claim 1, wherein the water content of the composition for removing edge bead is 1,000 ppm or less.

6. The organic solvent may be propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), propylene glycol butyl ether (PGBE), ethylene glycol methyl ether, diethyl glycol ethyl methyl ether, dipropyl glycol dimethyl ether, ethanol, 2-butoxyethanol, n-propanol, isopropanol, n-butanol, isobutyl alcohol, hexanol, ethylene glycol, propylene glycol, heptanone, propylene carbonate, butylene carbonate, diethyl ether, dibutyl ether, ethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diisopentyl ether, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, acetonitrile, diacetone alcohol, 3,3-dimethyl-2-butanone, N-methyl-2-pyrrolidone, dimethylacetamide, cyclohexanone methyl-2-hydroxy-2-methylpropanoate (HBM), gamma-butyrolactone (GBL), 1-butanol (n-butanol), ethyl lactate (EL), dibutyl ether (DBE), diisopropyl ether (DIAE), acetylacetone, butyl lactate (n-butyllactate), 4-methyl-2-pentanol (or methyl isobutyl carbinol (MIBC)), 1-methoxy-2-propanol, 1-ethoxy-2-propanol, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, methyl 2-hydroxyisobutyrate 2-hydroxyisobutyrate), methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate, or a mixture thereof.

7. 2. The composition for removing edge bead of a metal-containing resist according to claim 1, wherein the organic solvent is one selected from the group consisting of propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), 4-methyl-2-pentanol (also represented by methyl isobutyl carbinol (MIBC)), and mixtures thereof.

8. 2. The composition for removing edge bead of metal-containing resist of claim 1, wherein the organic solvent is propylene glycol methyl ether acetate (PGMEA).

9. 2. The composition for removing edge bead of metal-containing resist according to claim 1, wherein the metal compound is represented by the following chemical formula 1: 【Chemistry 1】 (In the above Chemical Formula 1, R １ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 or C30 arylalkyl group, and -R ａ -O-R ｂ (Here, R ａ is a substituted or unsubstituted C1 to C20 alkylene group, R ｂ is a substituted or unsubstituted C1-C20 alkyl group; R ２ ~R ４ are each independently -OR ｃ or -OC(=O)R ｄ is selected from R ｃ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R ｄ is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.

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