Composition for removing edge beads of metal-containing resist and pattern forming method including a step of removing edge beads using the same

Abstract

To provide a composition for removing edge beads of a metal-containing resist, in detail, a composition for removing edge beads of a metal-containing resist that minimizes a resist residue.SOLUTION: A composition for removing edge beads of a metal-containing resist includes: an additive including at least one selected from a group consisting of phosphoric acid, a phosphorous acid-based compound, and a hypophosphorous acid-based compound and a carboxylic acid-based compound; and an organic solvent. A mixing mass ratio of the at least one selected from the group consisting of the phosphoric acid, the phosphorous acid-based compound, and the hypophosphorous acid-based compound to the carboxylic acid-based compound is 9:1 to 1.2:1.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] In recent years, the semiconductor industry has been demanding new types of high performance photoresist materials and patterning methods to meet the demands of fabricating and patterning smaller and smaller features as critical dimensions continue to shrink.

[0003] Furthermore, with the recent rapid development of the semiconductor industry, there is a demand for improved operating speeds and larger memory capacities for semiconductor devices. To meet these demands, process technologies are being developed to improve the integration, reliability, and response speed of semiconductor devices. In particular, it is important to precisely control / inject impurities into active regions of silicon substrates and interconnect these regions to form elements and ultra-high density direct circuits, which is made possible by photolithography processes. That is, it is becoming increasingly important to consider the integration of photolithography processes, which include 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 applied to the edge and backside of the substrate, which can lead to indentation or pattern defects in subsequent semiconductor processes, such as etching and ion implantation. Therefore, a process for stripping and removing the photoresist applied to the edge and backside of the silicon substrate, i.e., edge bead removal (EBR), is performed using a thinner composition. The EBR process requires a composition that exhibits excellent photoresist solubility and effectively removes the beads and photoresist remaining on the substrate, leaving little or no resist residue. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Korean Patent Publication No. 2016-0078701 [Patent Document 2] Korean Patent Publication No. 2022-0115510 [Patent Document 3] International Publication No. 2019 / 073931 Summary of the Invention [Problem to be solved by the invention]

[0006] SUMMARY OF THE INVENTION An object of the present invention is to provide a composition for removing edge beads of metal-containing resist, and more particularly, to provide a composition for removing edge beads of metal-containing resist that minimizes resist residue.

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

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

[0009] The mixing mass ratio of at least one of the phosphoric acid, phosphorous acid compound and hypophosphorous acid compound to the carboxylic acid compound may be 9:1 to 6:4.

[0010] The content of the additive may be 0.01 to 50 mass % and the content of the organic solvent may be 50 to 99.99 mass % relative to 100 mass % of the total mass of the composition for removing edge beads of a metal-containing resist.

[0011] The content of at least one compound selected from the group consisting of phosphoric acid, phosphorous compounds, and hypophosphorous compounds may be 0.005 to 10 mass % relative to the total mass of the composition for removing edge beads of metal-containing resist (100 mass %).

[0012] The content of the 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 of metal-containing resist.

[0013] The phosphorous acid 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.

[0014] The hypophosphorous acid 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 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.

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

[0017] The organometallic compound contained in the metal-containing resist can include at least one of an organic oxy group-containing tin compound and an organic carbonyloxy group-containing tin compound.

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

[0019] [ka]

[0020] In the above chemical formula 1, R 1 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 -OR 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 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, -OR b or -OC(=O)R c and In this case, R 2 ~R 4 At least one of -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 cis 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.

[0021] A pattern forming method according to another embodiment of the present invention includes a step of applying a metal-containing resist onto a substrate, a step of applying the above-described composition for removing edge beads of a 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, a step of exposing the metal-containing resist film, and a development step. [Effects of the Invention]

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

[0023] [Figure 1] FIG. 1 is a schematic diagram illustrating an example of a photoresist coating apparatus. [Figure 2] 1 is a photograph of a thin photoresist film taken in a profiler device after an edge bead removal composition is sprayed onto the photoresist film on a silicon wafer. [Figure 3] FIG. 3 is a schematic diagram of the hump shown in FIG. 2. DETAILED DESCRIPTION OF THE INVENTION

[0024] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, in describing the present invention, descriptions of already known functions or configurations will be omitted in order to clarify the gist of the present invention.

[0025] In order to clearly explain the present invention, parts that are not relevant to the explanation will be omitted, and the same or similar components will be denoted 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 explanation, and the present invention is not necessarily limited to those shown in the drawings.

[0026] In the drawings, thicknesses of multiple layers and regions are exaggerated to clearly show them. Also, for the convenience of explanation, the thicknesses of some layers and regions are exaggerated. When a layer, film, region, plate, or other portion is "on" or "on" another portion, this includes not only when it is "directly on" the other portion, but also when there is another portion between them.

[0027] In this specification, "substituted" means that a hydrogen atom is substituted with a deuterium atom, a halogen atom, a hydroxy group, an amino group, a substituted or unsubstituted organic amino group having 1 to 30 carbon atoms, a nitro group, a substituted or unsubstituted organic 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 the hydrogen atom is not substituted with another substituent and remains as a hydrogen atom.

[0028] In this specification, unless otherwise defined, the term "alkyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double 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, for example, at least one selected from the group consisting of 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 the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group.

[0031] In this specification, unless otherwise defined, the term "cycloalkyl group" refers to a monovalent alicyclic hydrocarbon group.

[0032] Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0033] In this specification, unless otherwise defined, the term "alkenyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group and an aliphatic unsaturated alkenyl group containing one or more double bonds.

[0034] As used herein, unless otherwise defined, the term "alkynyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group and an aliphatic unsaturated alkynyl group containing one or more triple bonds.

[0035] As used herein, the term "aryl group" refers to a substituent in which all elements of the cyclic substituent have p-orbitals and these p-orbitals form conjugation, and includes monocyclic or fused polycyclic (i.e., rings that share adjacent pairs of carbon atoms) functional groups.

[0036] More specifically, the substituted or unsubstituted aryl group having 6 to 30 carbon atoms may be, but is not limited to, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted o-terphenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted benzophenanthrenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, or a combination thereof.

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

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

[0039] 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 a standby area away from the top of the substrate (W) and moves to the top of the substrate during the solution supply step to spray a photoresist solution (metal-containing resist) 10. As a result, the photoresist solution (metal-containing resist) 10 is applied to the surface of the substrate by centrifugal force. At this time, the photoresist solution (metal-containing resist) 10 supplied to the center of the substrate (W) spreads to the edge of the substrate (W) by centrifugal force, and some of it moves to the side of the substrate and the underside of the edge of the substrate.

[0040] That is, in the coating process, the photoresist solution (metal-containing resist) 10 is mainly applied by spin coating, and 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 edge 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 and the surface tension causes a relatively large amount of resist to accumulate at the edge of the substrate, and even more seriously, the resist may accumulate on the underside of the edge of the substrate. This type of resist accumulation is called an edge bead (12 in Figure 1).

[0043] A composition for removing edge beads of a metal-containing resist according to one embodiment of the present invention will be described below.

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

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

[0046] In addition, it is possible to minimize film deterioration by minimizing humps that cause resist cracks and peeling. Hump (b) refers to the increase in film thickness (ΔThickness) that occurs at the boundary with the removed part after removing the edge bead, as shown in Figure 3.

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

[0048] In one embodiment, the composition for removing edge beads of a metal-containing resist can contain the additives described above in a content of 0.01 to 50% by mass, and an organic solvent in a content of 50 to 99.99% by mass.

[0049] More specifically, in one embodiment, the additive may be contained in an amount of 0.05 to 50 mass%, 0.1 to 50 mass%, 0.1 to 40 mass%, 0.1 to 30 mass%, 0.1 to 20 mass%, or 0.1 to 10 mass%, relative to 100 mass% of the total mass of the composition for removing edge beads of metal-containing resist.

[0050] In one embodiment, the organic solvent may be contained in an amount of 50 to 99.95 mass%, 50 to 99.9 mass%, 60 to 99.9 mass%, 70 to 99.9 mass%, 80 to 99.9 mass%, or 90 to 99.9 mass%, relative to 100 mass% of the total mass of the composition for removing edge beads of metal-containing resist.

[0051] In one embodiment, the composition for removing edge beads of metal-containing resist may contain at least one compound selected from the group consisting of phosphoric acid, phosphorous acid compounds, and hypophosphorous acid compounds in an amount of 0.005 to 10 mass % relative to the total mass of the composition (100 mass %).

[0052] More specifically, the composition for removing edge beads of metal-containing resist may contain at least one compound selected from the group consisting of phosphoric acid, phosphorous acid compounds, and hypophosphorous acid compounds in an amount of, for example, 0.01 to 5 mass%, for example, 0.1 to 5 mass%, for example, 0.5 to 3 mass%, relative to 100 mass% of the total mass of the composition.

[0053] In one embodiment, the carboxylic acid compound may be contained 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 of a metal-containing resist.

[0054] More specifically, the carboxylic acid compound may be contained in an amount of, for example, 0.01 to 5 mass%, for example, 0.1 to 5 mass%, for example, 0.1 to 2 mass%, relative to 100 mass% of the total mass of the composition for removing edge beads of metal-containing resist.

[0055] The phosphorous acid 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 hypophosphorous acid 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 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 composition for removing edge beads of a metal-containing resist 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 area that comes into contact with the photoresist, resulting in deterioration of the film.

[0060] Examples of organic solvents contained in the composition for removing edge beads of a metal-containing resist according to one embodiment of the present invention 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, n-hexanol, ethylene glycol, propylene glycol, n-heptanone, propylene carbonate, butylene carbonate, and diethyl ether. ter, 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, γ-butyrolactone (GBL), 1-butanol, ethyl lactate, dibutyl ether, diisopropyl ether, acetylacetone, butyl lactate, 4-methyl-2-pentanol (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, 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 of the present invention is particularly effective for removing metal-containing resists, and more specifically, undesirable metal residues, such as tin-based metal residues.

[0062] When other additives described below are contained, the organic solvent may be contained in an amount that is the balance excluding the contained components.

[0063] The composition for removing edge beads of a metal-containing resist according to the present invention may further contain at least one other additive selected from the group consisting of a surfactant, a dispersant, a moisture absorbent, and a coupling agent.

[0064] The organometallic compound contained in the metal-containing resist can include at least one of an organic oxy group-containing tin compound and an organic carbonyloxy group-containing tin compound.

[0065] For example, the organometallic compound contained in the metal-containing resist can be a compound represented by the following Chemical Formula 1 or a condensation product thereof:

[0066] [ka]

[0067] In the above chemical formula 1, R 1 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 -OR 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 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, -OR b or -OC(=O)R c and In this case, R 2 ~R 4 At least one of -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 c is 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.

[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, there is provided a method for forming a pattern, comprising removing edge beads using the above-described composition for removing edge beads of a metal-containing resist. For example, the formed pattern may be a photoresist pattern. More specifically, it may be a negative photoresist pattern.

[0070] A pattern forming method according to one embodiment includes the steps of applying a metal-containing resist onto a substrate, applying the above-described composition for removing edge beads of 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, exposing the metal-containing resist film to light, and developing the metal-containing resist film to form a resist pattern.

[0071] The process of forming a pattern using a metal-containing resist first involves applying the metal-containing resist to a substrate. More specifically, the process can include applying the metal-containing resist to a substrate on which a thin film has been formed by spin coating, slit coating, inkjet printing, or the like, and then drying the applied metal-containing resist to form a photoresist film. The metal-containing resist can include a tin-containing compound, and for example, the tin-based compound can include at least one of an organic oxy group-containing tin compound and an organic carbonyloxy group-containing tin compound.

[0072] For example, the organometallic compound contained in the metal-containing resist may be a compound represented by Chemical Formula 1 above.

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

[0074] Subsequently, a first heat treatment step is performed to heat the substrate on which the photoresist film is formed. The first heat treatment step can be performed at a temperature of 80°C to 120°C, during which the solvent evaporates and the photoresist film can be more firmly attached to the substrate.

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

[0076] For example, examples of light that can be used in the exposure process include light with short wavelengths such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), as well as light with high-energy wavelengths 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 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 step of forming a photoresist pattern, a negative pattern can be formed.

[0079] The exposed regions of the photoresist film form polymers through crosslinking reactions such as condensation between organometallic compounds, resulting in a difference in solubility from the unexposed regions of the photoresist film.

[0080] Subsequently, the substrate is subjected to a second heat treatment step, which can be carried out at a temperature of 90° C. to 200° C. By carrying out the second heat treatment step, the exposed area of ​​the photoresist film becomes less soluble in a developer.

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

[0082] 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 monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, and γ-butyrolactone; aromatic compounds such as benzene, xylene, and toluene; and combinations thereof.

[0083] 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 Ultra Violet; wavelength 13.5 nm) and E-Beam (electron beam), can have widths of 5 nm to 100 nm. For example, photoresist patterns can be formed with widths 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.

[0084] On the other hand, the photoresist pattern can have a half-pitch of 50 nm or less, such as 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 with a line width roughness of 10 nm or less, 5 nm or less, 3 nm or less, 2 nm or less. [Example]

[0085] The present invention will be described in more detail below through examples of preparing the composition for removing edge beads of metal-containing resists. However, the technical features of the present invention are not limited to the following examples.

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

[0087] Manufacturing example: Manufacturing of metal-containing resist An organometallic compound containing a structural unit represented by the following chemical formula C was dissolved in 4-methyl-2-pentanol at a concentration of 1 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 residual Sn 2.0 mL of the metal-containing resist obtained in the above manufacturing example was applied to a 6-inch silicon wafer, allowed to stand for 20 seconds, and then spin-coated at 1500 rpm for 30 seconds. The wafer was then heat-treated at 200°C for 60 seconds, and the thickness of the resulting coating film was measured using spectroscopic ellipsometry. 10 mL of each of the metal-containing resist edge bead removal compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 4 was applied along the edge of the wafer on which the coating film had been formed, spin-coated for 5 seconds, and then dried by rotating at 1500 rpm. The amount of residual Sn was then determined for the resulting film 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 Preparation Example was applied to a 6-inch silicon wafer, left to stand for 20 seconds, and then spin-coated at 1500 rpm for 30 seconds. The edge bead removal compositions according to Examples 1 to 3 and Comparative Examples 1 to 4, prepared as shown in Table 1 below, were then sprayed onto the wafer at a point 1 mm from the outer periphery at a flow rate of 10 mL / min for 5 seconds.

[0091] Figure 2 is a photograph of a thin photoresist film on a silicon wafer after a composition for removing edge beads of a metal-containing resist has been sprayed onto the thin photoresist film in a profiler device, and Figure 3 is a schematic diagram of the hump shown in Figure 2.

[0092] 2 and 3, "hump" refers to the ΔThickness(Hump) that occurs when the edge of a thin film of metal-containing resist is convex after spraying the composition for removing edge bead of metal-containing resist. The ΔThickness(Hump) values ​​measured using a Tencor Profiler P17OF device are listed in Table 1 below.

[0093] [Table 1]

[0094] Referring to Table 1, it can be seen that the compositions for removing edge beads of metal-containing resist according to Examples 1 to 3 have a superior metal removal effect compared to the compositions for removing edge beads of metal-containing resist according to Comparative Examples 1 to 4, and can further promote the reduction of residual metal.

[0095] Furthermore, it can be confirmed that the compositions for removing edge beads of metal-containing resist according to Examples 1 to 3 have superior metal removal effects and lower hump compared to the compositions for removing edge beads of metal-containing resist according to Comparative Examples 1 to 4.

[0096] While specific embodiments of the present invention have been described and illustrated above, the present invention is not limited to the described embodiments, and it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modifications or variations should not be understood separately from the technical spirit or perspective of the present invention, and the modified embodiments should be considered to fall within the scope of the claims of the present invention. [Explanation of symbols]

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

Claims

1. an additive containing at least one selected from the group consisting of phosphoric acid, a phosphorous compound, and a hypophosphorous compound, and a carboxylic acid compound; an organic solvent; Including, a mixing mass ratio of the at least one compound selected from the group consisting of phosphoric acid, a phosphorous compound, and a hypophosphorous compound to the carboxylic acid compound is 9:1 to 1.2:

1.

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

4.

3. With respect to 100% by mass of the total mass of the composition for removing edge beads of the metal-containing resist, The content of the additive is 0.01 to 50% by mass, 2. The composition for removing edge beads of a metal-containing resist according to claim 1, wherein the content of the organic solvent is 50 to 99.99% by mass.

4. 2. The composition for removing edge beads of metal-containing resist according to claim 1, wherein the content of the at least one compound selected from the group consisting of phosphoric acid, a phosphorous acid compound, and a hypophosphorous acid compound is 0.005 to 10 mass % relative to 100 mass % of the total mass of the composition for removing edge beads of metal-containing resist.

5. 2. The composition for removing edge beads of metal-containing resist according to claim 1, wherein the content of the carboxylic acid compound is 0.001 to 5 mass % relative to 100 mass % of the total mass of the composition for removing edge beads of metal-containing resist.

6. 2. The composition for removing edge beads of a metal-containing resist according to claim 1, wherein the phosphorous acid 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.

7. 2. The composition for removing edge beads of a metal-containing resist according to claim 1, wherein the hypophosphorous acid 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. 2. The composition for removing edge beads of 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. 2. The composition for removing edge beads of a metal-containing resist according to claim 1, wherein the water content in the composition for removing edge beads is 1,000 ppm by mass or less.

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

11. 2. The composition for removing edge beads of a metal-containing resist 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 above Chemical Formula 1, R １ 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 (Here, L ａ 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 independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, -OR ｂ or -OC(=O)R ｃ and At this time, R ２ ~R ４ At least one of the following 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 ｃ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof.

12. applying a metal-containing resist onto a substrate; A step of applying the composition for removing edge beads of metal-containing resist 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; exposing the metal-containing resist film to light; and A pattern forming method including a development step.

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