A composition for removing edge beads from a metal-containing resist, and a pattern forming method including a step of removing edge beads using the same.

Abstract

The present invention provides a composition for removing edge beads from metal-containing resists, and more specifically, a composition for removing edge beads from metal-containing resists that minimizes resist residue. [Solution] A composition for removing edge beads from metal-containing resists, comprising an additive containing at least one selected from the group consisting of phosphoric acid, phosphite compounds, and hypophosphite compounds, as well as a carboxylic acid compound, and an organic solvent, wherein the mixed mass ratio of at least one selected from the group consisting of phosphoric acid, phosphite compounds, and hypophosphite compounds to the carboxylic acid compound is 9:1 to 1.2:1.

Description

[Technical Field]

[0001] The present invention relates to a composition for removing edge beads from a metal-containing resist, and to a pattern forming method that includes a step of removing edge beads using the same. [Background technology]

[0002] In recent years, the semiconductor industry has seen a continuous decline in critical size, leading 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, there is a demand for increased operating speed and large storage capacity of semiconductor devices. In response to these demands, process technologies 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 the silicon substrate and to interconnect these regions to form elements and ultra-high-density direct circuits, which can be achieved through the photolithography process. That is, it is important to consider integrating the photolithography process, which involves coating a photoresist onto the substrate, selectively exposing it by irradiating it with ultraviolet light (including extreme ultraviolet light), electron beams, or X-rays, and then developing it.

[0004] In particular, during the process of forming the photoresist layer, the resist is mainly applied to the silicon substrate while it is rotating. However, in this process, the resist is applied to the substrate edges and the back surface, which can cause indentation or pattern defects in subsequent semiconductor processes such as etching and ion implantation. Therefore, a process called edge bead removal (EBR) is performed to strip and remove the photoresist applied to the edges and back surface of the silicon substrate using a thinner composition. In the EBR process, a composition is required that exhibits excellent solubility for photoresist and effectively removes beads and photoresist remaining on the substrate, resulting in little to no resist residue. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Korean Published Patent Publication No. 2016-0078701 [Patent Document 2] Korean Published Patent Publication No. 2022-0115510 [Patent Document 3] International Publication No. 2019 / 073931 [Overview of the project] [Problems that the invention aims to solve]

[0006] The object of the present invention is to provide a composition for removing edge beads from metal-containing resists, and more particularly, a composition for removing edge beads from metal-containing resists that minimizes resist residue.

[0007] Another object of the present invention is to provide a pattern forming method, more particularly a pattern forming method including an edge bead removal step. [Means for solving the problem]

[0008] A composition for removing edge beads from a metal-containing resist according to one embodiment of the present invention comprises an additive containing at least one selected from the group consisting of phosphoric acid, phosphite compounds, and hypophosphite compounds, as well as a carboxylic acid compound, and an organic solvent. The mass ratio of the mixture of at least one compound selected from the group consisting of phosphoric acid, phosphite compounds, and hypophosphite compounds, and the carboxylic acid compound is 9:1 to 1.2:1.

[0009] The mass ratio of at least one of the above-mentioned phosphoric acid, phosphite-based compounds, and hypophosphite-based compounds to the carboxylic acid-based compound may be 9:1 to 6:4.

[0010] The content of the above additive is 0.01 to 50% by mass of the total mass of the metal-containing resist edge bead removal composition, and the content of the above organic solvent can be 50 to 99.99% by mass.

[0011] The content of at least one selected from the group consisting of phosphoric acid, phosphite compounds, and hypophosphite compounds may be 0.005 to 10% by mass, relative to 100% by mass of the total mass of the composition for removing edge beads from metal-containing resists.

[0012] The content of the above carboxylic acid compound may be 0.001 to 5% by mass relative to 100% by mass of the total mass of the composition for removing edge beads from metal-containing resists.

[0013] The above phosphorous acid-based compound may be at least one selected from the group consisting 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, and 1H,1H,2H,2H-perfluorooctane phosphonic acid.

[0014] The above hypophosphorous acid-based compound may be at least one selected from the group consisting of phosphinic acid, phenylphosphinic acid, diphenylphosphinic acid, bis(4-methoxyphenyl)phosphinic acid, bis(hydroxymethyl)phosphinic acid, and p-(3-aminopropyl)-p-butylphosphinic acid.

[0015] The above carboxylic acid-based compound may be at least one selected from the group consisting of acetic acid, formic acid, propionic acid, butyric acid, valeric acid, caproic acid, and benzoic acid.

[0016] The water content in the above composition for removing edge beads may be 1,000 mass ppm or less.

[0017] The organometallic compound contained in the above metal-containing resist may contain at least one of an organooxy group-containing tin compound and an organic carbonyloxy group-containing tin compound.

[0018] The organometallic compound contained in the above metal-containing resist is preferably a compound represented by the following Chemical Formula 1 or a condensate thereof.

[0019]

Chemical formula

[0020] In the above Chemical Formula 1, R , b , c is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, or L a -O-R a (where L a is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, and R a is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms), R 2 ~R 4 are each 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, a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, -OR b or -OC(=O)R c and at this time, at least one of R 2 ~R 4 is -OR b or -OC(=O)R c and R b is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof, R cThese are hydrogen atoms, 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, or combinations thereof.

[0021] Another embodiment of the present invention provides a pattern forming method which includes the steps of: applying a metal-containing resist onto a substrate; applying the above-mentioned edge bead removal composition for the metal-containing resist along the edge of the substrate; a heat treatment step which involves drying and heating to form a metal-containing resist film on the substrate; an exposure step which involves exposing the metal-containing resist film; and a development step. [Effects of the Invention]

[0022] According to the present invention, a composition for removing edge beads from metal-containing resists is provided, and more particularly, a composition for removing edge beads from metal-containing resists that minimizes resist residue is provided. [Brief explanation of the drawing]

[0023] [Figure 1] This is a schematic diagram showing an example of a photoresist coating apparatus. [Figure 2] This is a photograph of a photoresist thin film on a silicon wafer after an edge bead removal composition has been sprayed onto the photoresist film using a profiler device. [Figure 3] Figure 2 is a schematic diagram of a hump. [Modes for carrying out the invention]

[0024] 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 already known functions or configurations will be omitted.

[0025] To clearly explain the present invention, irrelevant parts have been omitted, and the same or similar components are given the same reference numerals throughout the specification. Furthermore, the dimensions and thicknesses of each component shown in the drawings are arbitrarily shown for the convenience of explanation, and the present invention is not necessarily limited to those shown.

[0026] 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.

[0027] In this specification, "substituted" means that a hydrogen atom is substituted with a deuterium atom, a halogen atom, a hydroxyl group, an amino group, a substituted or unsubstituted C1-C30 organic amino group, a nitro group, a substituted or unsubstituted C1-C40 organic silyl group, a C1-C30 alkyl group, a C1-C10 haloalkyl group, a C1-C10 alkylsilyl group, a C3-C30 cycloalkyl group, a C6-C30 aryl group, a C1-C20 alkoxy group, or a cyano group. "Unsubstituted" means that a hydrogen atom is not substituted with another substituent and remains a hydrogen atom.

[0028] 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.

[0029] The alkyl group may be an alkyl group having 1 to 20 carbon atoms. More specifically, the alkyl group may be an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. For example, an alkyl group having 1 to 5 carbon atoms means that the alkyl chain contains 1 to 5 carbon atoms, and may be at least one selected from the group consisting of, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group.

[0030] Specific examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, and n-hexyl group.

[0031] In this specification, "cycloalkyl group" means a monovalent alicyclic hydrocarbon group unless otherwise defined.

[0032] Examples of cycloalkyl groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups.

[0033] In this specification, "alkenyl group" means a linear or branched aliphatic hydrocarbon group containing one or more double bonds, which is an aliphatic unsaturated alkenyl group.

[0034] In this specification, "alkynyl group" means a linear or branched aliphatic hydrocarbon group containing one or more triple bonds, which is an aliphatic unsaturated alkynyl group.

[0035] 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.

[0036] More specifically, the substituted or unsubstituted C6-C30 aryl group may be, but is not limited to, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenantrenyl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted o-terphenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted benzophenantrenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perilennyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, or a combination thereof.

[0037] Figure 1 is a schematic diagram showing an example of a photoresist coating apparatus.

[0038] Referring to Figure 1, the photoresist coating apparatus is equipped with a substrate support section 1 on which a substrate (W) is placed, and the substrate support section 1 includes a spin chuck or a spin coater.

[0039] 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. The injection nozzle 2 is positioned in a standby area away from the top of the substrate (W), and can move to the top of the substrate during the solution supply stage to spray the photoresist solution (metal-containing resist) 10. As a result, the photoresist solution (metal-containing resist) 10 is applied to the substrate surface by centrifugal force. At this time, the photoresist solution (metal-containing resist) 10 supplied to the center of the substrate (W) is applied while spreading to the edges of the substrate (W) by centrifugal force, and a portion of it moves to the sides of the substrate and the underside of the edges of the substrate.

[0040] In other words, during the coating process, the photoresist solution (metal-containing resist) 10 is mainly coated by a spin coating method. A predetermined amount of viscous photoresist solution (metal-containing resist) 10 is supplied to the center of the substrate (W), and the photoresist solution (metal-containing resist) gradually spreads toward the edges of the substrate due to centrifugal force.

[0041] Therefore, the resist can be formed into a flat film depending on the rotation speed of the substrate support.

[0042] However, as the solvent evaporates, the viscosity increases further, and due to surface tension, a relatively large amount of resist accumulates at the edges of the substrate. Even more seriously, the resist accumulates all the way to the underside of the edges of the substrate. This type of resist accumulation is called an edge bead (12 in Figure 1).

[0043] The following describes a composition for removing edge beads from metal-containing resists according to one embodiment of the present invention.

[0044] A composition for removing edge beads from a metal-containing resist according to one embodiment of the present invention comprises an additive containing at least one selected from the group consisting of phosphoric acid, phosphite compounds, and hypophosphite compounds, as well as a carboxylic acid compound, and an organic solvent, wherein the mass ratio of the mixture of at least one selected from the group consisting of phosphoric acid, phosphite compounds, and hypophosphite compounds to the carboxylic acid compound is 9:1 to 1.2:1.

[0045] By further adding a carboxylic acid compound to at least one selected from the group consisting of phosphoric acid, phosphite compounds, and hypophosphite compounds, metal-containing resists, more specifically, undesirable metal residues, such as tin-based metal residues, can be removed more effectively.

[0046] Furthermore, by minimizing humps, which can cause cracking and delamination of the resist, film degradation can be minimized. A hump (b), as schematically illustrated in Figure 3, refers to the occurrence of an increase in film thickness (ΔThickness) at the boundary with the removed portion after edge beads have been removed.

[0047] For example, the mass ratio of the mixture of at least one compound selected from the group consisting of phosphoric acid, phosphite compounds, and hypophosphite compounds and a carboxylic acid compound may most specifically be 9:1 to 6:4.

[0048] In one embodiment, the composition for removing edge beads from metal-containing resists 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.

[0049] More specifically, in one embodiment, the additive can be included in an amount of 0.05 to 50% by mass, 0.1 to 50% by mass, 0.1 to 40% by mass, 0.1 to 30% by mass, 0.1 to 20% by mass, or 0.1 to 10% by mass, based on 100% by mass of the total mass of the composition for removing edge beads of metal-containing resists.

[0050] In one embodiment, the composition for removing edge beads from metal-containing resists may contain organic solvents in an amount of 50-99.95% by mass, 50-99.9% by mass, 60-99.9% by mass, 70-99.9% by mass, 80-99.9% by mass, or 90-99.9% by mass, based on 100% by mass of the total mass of the composition for removing edge beads from metal-containing resists.

[0051] In one embodiment, the edge bead removal composition for metal-containing resists may contain at least one selected from the group consisting of phosphoric acid, phosphite compounds, and hypophosphite compounds in an amount of 0.005 to 10% by mass, based on 100% by mass of the total mass.

[0052] More specifically, the composition for removing edge beads from metal-containing resists may contain, for example, 0.01 to 5% by mass, 0.1 to 5% by mass, or 0.5 to 3% by mass, based on 100% by mass of the total mass.

[0053] In one embodiment, the carboxylic acid compound may be included in an amount of 0.001 to 5% by mass relative to 100% by mass of the total mass of the composition for removing edge beads from metal-containing resists.

[0054] More specifically, the carboxylic acid compound can be included in an amount of, for example, 0.01 to 5% by mass, for example, 0.1 to 5% by mass, or for example, 0.1 to 2% by mass, based on 100% by mass of the total mass of the composition for removing edge beads from metal-containing resists.

[0055] The above-mentioned phosphite-based compound may be at least one selected from the group consisting 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, and 1H,1H,2H,2H-perfluorooctanephosphonic acid.

[0056] The above hypophosphorous compound may be at least one selected from the group consisting of phosphinic acid, phenylphosphinic acid, diphenylphosphinic acid, bis(4-methoxyphenyl)phosphinic acid, bis(hydroxymethyl)phosphinic acid, and p-(3-aminopropyl)-p-butylphosphinic acid.

[0057] The above carboxylic acid compound may be at least one selected from the group consisting of acetic acid, formic acid, propionic acid, butyric acid, valeric acid, caproic acid, and benzoic acid.

[0058] On the other hand, the water content of the metal-containing resist edge bead removal composition may be 1,000 ppm by mass or less.

[0059] If the water content in the composition exceeds 1,000 ppm by mass, hydration may occur in the areas in contact with the photoresist, potentially leading to deterioration of the film.

[0060] Examples of organic solvents included in the metal-containing resist edge bead removal composition according to one embodiment of the present invention include, for example, 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, n-hexanol, ethylene glycol, propylene glycol, n-heptanone, propylene carbonate, butylene carbonate, and diethyl ether. Tel, 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-methylpropanate, γ-butyrolactone (GBL), 1-butanol, ethyl lactate, dibutyl ether, diisopropyl ether, acetylacetone, butyl lactate, 4-methyl-2-pentanol (methyl Examples include, but are not limited to, 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, butyl acetate, methyl 2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate, or mixtures thereof.

[0061] The metal-containing resist edge bead removal composition according to the present invention is particularly effective in removing metal-containing resists, and more specifically, undesirable metal residues, such as tin-based metal residues.

[0062] If other additives described later are included, the above organic solvent may be included in the remainder of the components excluding those additives.

[0063] The metal-containing resist edge bead removal composition according to the present invention may further contain at least one other additive selected from the group consisting of surfactants, dispersants, hygroscopic agents, and coupling agents.

[0064] The organometallic compounds contained in the metal-containing resist may include at least one of an organooxy group-containing tin compound and an organocarbonyloxy group-containing tin compound.

[0065] For example, the organometallic compounds contained in the metal-containing resist may be compounds represented by the following chemical formula 1 or condensates thereof.

[0066] [ka]

[0067] In the above chemical formula 1, R 1 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-C31 arylalkyl groups, or L a -OR a (Here, L a R is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms. a (where is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms), R 2 ~R 4 Each of these independently comprises a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C31 arylalkyl group, and -OR b Or -OC(=O)R c And, In this case, R 2 ~R 4 At least one of them is -OR b Or -OC(=O)R c And, R b These are 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, or combinations thereof. R c These are hydrogen atoms, 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, or combinations thereof.

[0068] For example, the organometallic compound contained in the metal-containing resist may be at least one of an alkyloxy group-containing tin compound and an alkylcarbonyloxy group-containing tin compound.

[0069] According to another embodiment of the present invention, a pattern forming method can be provided that includes a step of removing edge beads using the metal-containing resist 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.

[0070] A pattern formation method according to one embodiment includes the steps of: applying a metal-containing resist onto a substrate; applying the above-mentioned edge bead removal composition for the metal-containing resist along the edge of the substrate; a heat treatment step of drying and heating to form a metal-containing resist film on the substrate; an exposure step of the metal-containing resist film; and a development step of forming a resist pattern.

[0071] The process of forming a pattern using a metal-containing resist first involves coating the substrate with the metal-containing resist. More specifically, this process may include coating the substrate with the metal-containing resist by spin coating, slit coating, inkjet printing, etc., and drying the coated metal-containing resist to form a photoresist film. The metal-containing resist may contain a tin-containing compound; for example, a 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.

[0072] For example, the organometallic compound contained in the above-mentioned metal-containing resist may be the compound represented by the above-mentioned chemical formula 1.

[0073] Next, a composition for removing edge beads from metal-containing resists is applied. More specifically, this step may include applying an appropriate amount of the aforementioned metal-containing resist edge bead removal composition along the edges of the substrate while rotating the substrate at an appropriate speed (e.g., 500 rpm or more) using a spin coating method or the like. By performing this step, the edge beads are removed.

[0074] 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 evaporates and the photoresist film can be more firmly bonded to the substrate.

[0075] Next, the photoresist film is selectively exposed.

[0076] For example, examples of light that can be used in the exposure process include not only short-wavelength light such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), but also high-energy wavelength light such as EUV (Extreme Ultra Violet; wavelength 13.5 nm) and E-Beam (electron beam).

[0077] 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 high-energy wavelength such as EUV (Extreme Ultra Violet, wavelength 13.5 nm) or E-Beam (electron beam).

[0078] In the process of forming a photoresist pattern, a negative type pattern can be formed.

[0079] 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.

[0080] Next, a second heat treatment process is performed on the substrate. This second heat treatment process can be carried out at a temperature of 90°C to 200°C. By performing this second heat treatment process, the exposed areas of the photoresist film become less soluble in the developer solution.

[0081] The development process can be carried out by using an organic solvent such as 2-heptanone to dissolve the photoresist film corresponding to the unexposed areas, and then removing it, thereby completing the photoresist pattern corresponding to the negative tone image.

[0082] The developer used in the pattern forming 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.

[0083] As mentioned above, photoresist patterns formed by exposure with light having wavelengths such as i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm), and ArF excimer laser (wavelength 193nm), as well as high-energy light such as EUV (Extreme Ultra Violet; wavelength 13.5nm) and E-Beam (electron beam), can have widths of 5nm to 100nm. For example, photoresist patterns can be formed with widths of 5nm to 90nm, 5nm to 80nm, 5nm to 70nm, 5nm to 60nm, 5nm to 50nm, 5nm to 40nm, 5nm to 30nm, and 5nm to 20nm.

[0084] On the other hand, the photoresist pattern can 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. [Examples]

[0085] The present invention will be described in more detail below through examples relating to the production of the metal-containing resist edge bead removal composition described above. However, the technical features of the present invention are not limited by the following examples.

[0086] (Examples 1-3 and Comparative Examples 1-4: Production of compositions for edge bead removal) The additives and solvents were mixed in the compositions shown in Table 1 below, and then shaken at room temperature (25°C) to completely dissolve them. Subsequently, the mixture was filtered using a PTFE (polytetrafluoroethylene) filter with a pore size of 1 μm to obtain the final composition for edge bead removal.

[0087] Manufacturing example: Manufacturing of metal-containing resists An organometallic compound containing the structural unit represented by the following chemical formula C was dissolved in 4-methyl-2-pentanol at a concentration of 1% by mass, and then filtered through a 0.1 μm PTFE syringe filter to produce a metal-containing resist.

[0088] [ka]

[0089] Evaluation 1: Evaluation of Sn residue 2.0 mL of the metal-containing resist obtained in 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 1500 rpm for 30 seconds. The thickness of the coating film obtained by heat treatment at 200°C for 60 seconds was then measured by spectroscopic ellipsometry. On the wafer with the coated film, 10 mL each of the edge bead removal compositions for metal-containing resist obtained from Examples 1 to 3 and Comparative Examples 1 to 4 was placed along the edge and spin-coated for 5 seconds, then dried by rotating at a speed of 1500 rpm. The amount of residual Sn was then confirmed on the film obtained by heat treatment at 150°C for 60 seconds by vapor-phase decomposition-inductively coupled plasma mass spectrometry (VPD-ICPMS), and the results are shown in Table 1.

[0090] Evaluation 2: Hump characteristic evaluation 2.0 mL of the metal-containing resist obtained in 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 1500 rpm for 30 seconds. Subsequently, the edge bead removal compositions according to Examples 1-3 and Comparative Examples 1-4, manufactured as shown in Table 1 below, were sprayed at a flow rate of 10 ml / min for 5 seconds at a point 1 mm from the outer edge of the wafer.

[0091] Figure 2 is a photograph of a photoresist thin film on a silicon wafer after a metal-containing resist edge bead removal composition has been sprayed onto the photoresist thin film using a profiler. Figure 3 is a schematic diagram of the hump shown in Figure 2.

[0092] Referring to Figures 2 and 3, "hump" refers to the ΔThickness(Hump) that is generated as a convex shape at the edge of the metal-containing resist thin film after spraying the edge bead removal composition for metal-containing resists. The ΔThickness(Hump) values ​​measured with Tencor's P17OF profiler are listed in Table 1 below.

[0093] [Table 1]

[0094] Referring to Table 1, it can be confirmed that the metal-containing resist edge bead removal compositions according to Examples 1 to 3 have superior metal removal effects compared to the metal-containing resist edge bead removal compositions according to Comparative Examples 1 to 4, and can further promote the reduction of residual metal.

[0095] Furthermore, the metal-containing resist edge bead removal compositions according to Examples 1-3 exhibit superior metal removal effectiveness and reduced hump compared to the metal-containing resist edge bead removal compositions according to Comparative Examples 1-4.

[0096] 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. Therefore, such modifications or variations should not be understood individually from the technical spirit or viewpoint of the present invention, and the modified embodiments should be considered to fall within the scope of the claims of the present invention. [Explanation of Symbols]

[0097] 1. Substrate support section, 2 spray nozzles, 10. Photoresist solution (metal-containing resist), 12 edge beads, a resist, b Hump (ΔThickness), c Si substrate.

Claims

1. Additives comprising at least one selected from the group consisting of phosphoric acid, phosphite compounds, and hypophosphite compounds, and a carboxylic acid compound, Organic solvents and Includes, A composition for removing edge beads from metal-containing resists, wherein the mixed mass ratio of at least one selected from the group consisting of phosphoric acid, phosphite compounds, and hypophosphite compounds to the carboxylic acid compound is 9:1 to 1.2:

1.

2. The composition for removing edge beads from a metal-containing resist according to claim 1, wherein the mixed mass ratio of at least one selected from the group consisting of phosphoric acid, phosphite compounds, and hypophosphite compounds to the carboxylic acid compound is 9:1 to 6:

4.

3. With respect to 100% of the total mass of the metal-containing resist edge bead removal composition, The content of the aforementioned additive is 0.01 to 50% by mass. The composition for removing edge beads from a metal-containing resist according to claim 1, wherein the content of the organic solvent is 50 to 99.99% by mass.

4. The metal-containing resist edge bead removal composition according to claim 1, wherein the content of at least one selected from the group consisting of phosphoric acid, phosphite compounds, and hypophosphite compounds is 0.005 to 10% by mass, based on 100% by mass of the total mass of the metal-containing resist edge bead removal composition.

5. The metal-containing resist edge bead removal composition according to claim 1, wherein the content of the carboxylic acid compound is 0.001 to 5% by mass with respect to 100% by mass of the total mass of the metal-containing resist edge bead removal composition.

6. The phosphite compound is at least one selected from the group consisting 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, and 1H,1H,2H,2H-perfluorooctanephosphonic acid, as described in claim 1, for removing edge beads from metal-containing resists.

7. The composition for removing edge beads from a metal-containing resist according to claim 1, wherein the hypophosphite compound is at least one selected from the group consisting of phosphinic acid, phenylphosphinic acid, diphenylphosphinic acid, bis(4-methoxyphenyl)phosphinic acid, bis(hydroxymethyl)phosphinic acid, and p-(3-aminopropyl)-p-butylphosphinic acid.

8. The composition for removing edge beads from a metal-containing resist according to claim 1, wherein the carboxylic acid compound is at least one selected from the group consisting of acetic acid, formic acid, propionic acid, butyric acid, valeric acid, caproic acid, and benzoic acid.

9. The edge bead removal composition for metal-containing resists according to claim 1, wherein the water content in the edge bead removal composition is 1,000 ppm by mass or less.

10. The metal-containing resist edge bead removal composition according to claim 1, wherein the organometallic compound contained in the metal-containing resist is at least one of an organic oxy group-containing tin compound and an organic carbonyl oxy group-containing tin compound.

11. The metal-containing resist edge bead removal composition according to claim 1, wherein the organometallic compound contained in the metal-containing resist is a compound represented by the following chemical formula 1 or a condensate thereof: 【Chemistry 1】 In the aforementioned chemical formula 1, R １ 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-C31 arylalkyl groups, or L ａ -O-R ａ (Here, L ａ (wherein is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, and Ra is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms), R ２ ~R ４ Each of these independently comprises a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C31 arylalkyl group, and -OR ｂ or -OC(=O)R ｃ And, At this time, R ２ ~R ４ At least one of which is -OR ｂ or -OC(=O)R ｃ and R ｂ These are 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, or combinations thereof. R ｃ These are a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof.

12. A process of applying a metal-containing resist onto a substrate; A step of applying the metal-containing resist edge bead removal composition according to any one of claims 1 to 11 along the edge of the substrate; A heat treatment step of drying and heating to form a metal-containing resist film on the substrate; A step of exposing the metal-containing resist film; and A pattern formation method including a development step.

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