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

Abstract

The present invention provides a composition for removing edge bead of a metal-containing resist, the composition comprising an organic solvent and a cyclic compound substituted with at least one hydroxyl group (-OH), the cyclic compound having 5 to 30 carbon atoms and at least one double bond in the ring, and a pattern formation method including an edge bead removal step using the same. JPEG2024528807000018.jpg94170

Description

[Technical field]

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

[0002] In recent years, the semiconductor industry has experienced a continuous decrease in critical dimensions, which has required new types of high performance photoresist materials and patterning methods to meet the needs of fabricating and patterning ever-increasingly small features.

[0003] In addition, with the recent rapid development of the semiconductor industry, semiconductor devices are required to have higher operating speeds and larger memory capacities, and 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 the active regions of the silicon substrate so that these regions are interconnected to form elements and ultra-high density direct circuits, which can be achieved through the photolithography process. In other words, it is becoming important to consider incorporating the photolithography process, which involves coating a photoresist on a substrate, selectively exposing it to ultraviolet rays (including extreme ultraviolet rays), electron beams, or X-rays, and then developing it.

[0004] In particular, in the process of forming a photoresist layer, the resist is applied onto the substrate while the substrate is rotated, and in this process, the resist is also applied to the edge and back surface of the substrate, which may cause indentation 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 back surface of the silicon substrate using a thinner composition, i.e., an edge bead removal (EBR) process, is performed. In the EBR process, a composition that has excellent solubility in photoresist and effectively removes beads and photoresist remaining on the substrate without generating resist residue is required. Summary of the Invention [Problem to be solved by the invention]

[0005] One embodiment provides a composition for removing edge bead of a metal-containing resist.

[0006] Another embodiment provides a method for forming a pattern, comprising removing edge beading using the composition. [Means for solving the problem]

[0007] According to one embodiment, a composition for removing edge bead of a metal-containing resist includes an organic solvent and a cyclic compound substituted with at least one hydroxyl group (-OH), the cyclic compound having 5 to 30 carbon atoms and at least one double bond in the ring.

[0008] The cyclic compounds may be substituted with one or two hydroxy groups (-OH).

[0009] The cyclic compound has 5 to 20 carbon atoms.

[0010] The cyclic compound has 5 to 10 carbon atoms.

[0011] The cyclic compound is represented by any one of the following chemical formulas 1 to 3. [ka]

[0012] In the above Chemical Formulas 1 to 3, R 1 ~R 17 are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group; R 1 ~R 6 At least one of R 7 ~R 11 At least one of, and R 12 ~R 17 At least one of these is a hydroxy group.

[0013] The cyclic compound may be selected from the chemical formulas shown in Group 1 below. [ka]

[0014] In the above Group 1, R 1 ~R 17 are each independently a hydrogen atom, a halogen atom, an amino group, a substituted or unsubstituted C1 to C30 amine group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

[0015] The cyclic compound may be selected from the compounds shown in Group 2 below. [ka]

[0016] The composition for removing edge beads of a metal-containing resist can contain 50 to 99.99% by weight of an organic solvent; and 0.01 to 50% by weight of a cyclic compound.

[0017] The metal compound contained in the metal-containing resist may contain at least one of an alkyltin oxo group and an alkyltin carboxyl group.

[0018] The metal compound contained in the metal-containing resist is represented by the following chemical formula 4. [ka]

[0019] In the above Chemical Formula 4, R 18 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 to C30 arylalkyl group, and -R a -OR b (where R a is a substituted or unsubstituted C1 to C20 alkylene group, R b is a substituted or unsubstituted C1 to C20 alkyl group; R 19 ~R 21 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.

[0020] A method for forming a pattern according to another embodiment includes the steps of applying a metal-containing resist composition onto a substrate, applying the above-described composition for removing edge beads of a metal-containing resist 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 performing exposure and development to form a resist pattern.

[0021] The method for forming a pattern may further include applying the above-described composition for removing edge beads of a metal-containing resist along an edge of the substrate after exposure and development. Effect of the Invention

[0022] The composition for removing edge beads of metal-containing resist according to an embodiment can reduce metal-based contamination inherent in metal-containing resist and remove resist applied to the edge and backside of a substrate, thereby meeting the needs of processing and patterning of smaller features. [Brief description of the drawings]

[0023] [Figure 1] FIG. 1 is a schematic diagram showing a photoresist coating apparatus. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0025] In order to clearly explain the present invention, parts unnecessary for the explanation will be omitted, and the same or similar components will be given the same reference numerals throughout the specification. In addition, the size and thickness of each component shown in the drawings are arbitrarily shown for the convenience of explanation, and the present invention is not necessarily limited to those shown.

[0026] In the drawings, the 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 part such as a layer, film, region, plate, etc. is "on" or "on" another part, this includes not only the case where it is "directly on" the other part, but also the case where there is another part between them.

[0027] In this description, "substituted" means that the hydrogen atom is replaced with deuterium, a halogen group, a hydroxyl group, an amino group, a substituted or unsubstituted C1-C30 amine group, a nitro group, a substituted or unsubstituted C1-C40 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 the hydrogen atom is not replaced with another substituent and remains a hydrogen atom.

[0028] In this description, unless otherwise defined, a "cyclic compound" refers to a compound having a structure in which terminal atoms constituting the molecule are linked to each other to form a ring, and can be classified into a "carbocyclic compound" and a "heterocyclic compound" depending on the type of atoms forming the ring.

[0029] The term "carbocyclic compound" refers to a compound in which the ring atoms are only carbon.

[0030] The "heterocyclic compound" refers to a compound containing heteroatoms other than carbon as ring-forming atoms.

[0031] Examples of heteroatoms that may be contained in the "heterocyclic compound" include, but are not limited to, N, O, S, P, and Si.

[0032] In this description, unless otherwise specified, an "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.

[0033] The alkyl group is a C1-C20 alkyl group. More specifically, the alkyl group may be a C1-C10 alkyl group or a C1-C6 alkyl group. For example, a C1-C4 alkyl group means one containing 1 to 4 carbon atoms in the alkyl chain, and is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, and t-butyl.

[0034] Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0035] In this description, unless otherwise defined, a "cycloalkyl group" refers to a monovalent cyclic aliphatic hydrocarbon group.

[0036] In this description, unless otherwise defined, the term "alkenyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group that is an aliphatic unsaturated alkenyl group containing one or more double bonds.

[0037] In this description, unless otherwise defined, the term "alkynyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group that is an aliphatic unsaturated alkynyl group containing one or more triple bonds.

[0038] In this description, an "aryl group" means a substituent in which all elements of the substituent that are cyclic have p-orbitals and these p-orbitals form conjugation, including monocyclic or fused-ring polycyclic (i.e., rings that share adjacent pairs of carbon atoms) functional groups.

[0039] FIG. 1 is a schematic diagram showing a photoresist coating apparatus.

[0040] 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.

[0041] The substrate support 1 rotates in a first direction at a predetermined rotation speed to provide a centrifugal force to the substrate (W).

[0042] A spray nozzle 2 is positioned on the substrate support 1, and the spray nozzle 2 is located in a standby area away from the top of the substrate (W) and 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 edge of the substrate (W) by the centrifugal force and applied, and some of it moves to the side of the substrate and the underside of the edge of the substrate.

[0043] That is, in the coating process, the photoresist solution 10 is mainly coated by spin coating, in which a predetermined amount of viscous photoresist solution 10 is applied to the center of the substrate (W) and gradually spreads toward the periphery of the substrate by centrifugal force.

[0044] Therefore, the thickness of the photoresist is formed evenly depending on the rotation speed of the substrate support.

[0045] However, as the solvent evaporates and the viscosity increases, a relatively large amount of photoresist accumulates at the edge of the substrate due to the action of surface tension. Even more seriously, the photoresist accumulates on the underside of the edge of the substrate, which is called an edge bead 12.

[0046] Hereinafter, a composition for removing edge bead of a metal-containing resist according to an embodiment will be described.

[0047] A composition for removing edge bead of a metal-containing resist according to an embodiment of the present invention includes an organic solvent and a cyclic compound substituted with at least one hydroxyl group (-OH), the cyclic compound having 5 to 30 carbon atoms and at least one double bond in the ring.

[0048] The "double bond" is at least one contained in a ring, and due to the characteristics of the rigid structure of a cyclic compound, a form in which double bonds are contained consecutively is excluded, and "having at least one double bond in a ring" means that one double bond is contained via at least one single bond.

[0049] The composition for removing edge beads of metal-containing resist contains a cyclic compound substituted with a hydroxyl group (-OH), and the hydroxyl group (-OH) forms a coordinate bond with the resist containing the metal, so that the resist containing the metal can be effectively removed by applying the composition containing this.

[0050] As an example, the cyclic compound may be substituted with one or two hydroxy groups (-OH).

[0051] The cyclic compound may have 5 to 20 carbon atoms, for example, 5 to 10 carbon atoms.

[0052] For example, the cyclic compound may have 6 to 20 carbon atoms.

[0053] As a specific example, the cyclic compound may have 6 to 10 carbon atoms.

[0054] As an example, the cyclic compound is represented by any one of the following chemical formulas 1 to 3. [ka]

[0055] In the above Chemical Formulas 1 to 3, R 1 ~R 17 are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group; R 1 ~R 6 At least one of R 7 ~R 11 At least one of, and R 12 ~R 17 At least one of the groups is a hydroxy group.

[0056] As a specific example, the cyclic compound may be selected from the chemical formulas shown in Group 1 below. [ka]

[0057] In the above Group 1, R 1 ~R 17 are each independently a hydrogen atom, a halogen atom, an amino group, a substituted or unsubstituted C1 to C30 amine group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

[0058] For example, the cyclic compound may be selected from the compounds shown in Group 2 below. [ka]

[0059] In one embodiment, the composition for removing edge beads of a metal-containing resist may contain 50 to 99.99 wt % of an organic solvent and 0.01 to 50 wt % of the cyclic compound.

[0060] In a specific embodiment, the composition for removing edge beads of a metal-containing resist may contain the above-mentioned cyclic compound in an amount of 0.05 to 40 wt %, specifically 0.5 to 30 wt %, more specifically 1 to 20 wt %.

[0061] Examples of organic solvents included in the composition for removing edge beads of a metal-containing resist according to an 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, dipropylene 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-methylpropionate (HBM), gamma-butyrolactone (GBL), 1-butanol (n-Butanol), ethyl lactate (EL), diethyl butyl 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, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate Examples of suitable alkoxy groups include, but are not limited to, 2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate, or mixtures thereof.

[0062] The metal-containing resist edge bead removal compositions of the present invention are particularly effective in removing metal-containing resists, and more specifically, undesirable metal residues, such as tin-based metal residues.

[0063] The metal compound contained in the metal-containing resist may contain at least one of an alkyltin oxo group and an alkyltin carboxyl group.

[0064] As an example, the metal compound contained in the metal-containing resist is represented by the following chemical formula 4. [ka]

[0065] In the above Chemical Formula 4, R 18 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 to C30 arylalkyl group, and -R a -OR b (where R a is a substituted or unsubstituted C1 to C20 alkylene group, R b is a substituted or unsubstituted C1 to C20 alkyl group; R 19 ~R 21 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.

[0066] Meanwhile, according to another embodiment, there may be provided a method for forming a pattern, comprising removing edge beads using the above-mentioned composition for removing edge beads of a metal-containing resist. For example, the manufactured pattern may be a photoresist pattern. More specifically, it may be a negative photoresist pattern.

[0067] According to one embodiment, the method for forming a pattern includes the steps of applying a metal-containing resist composition onto a substrate, applying the composition for removing edge beads of the metal-containing resist 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 performing exposure and development to form a resist pattern.

[0068] More specifically, the step of forming a pattern using the metal-containing resist composition may include a step of 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 a step of 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.

[0069] More specifically, the method may include applying an appropriate amount of the composition for removing edge beads of a metal-containing resist along the edge of the substrate while spinning the substrate at an appropriate speed (e.g., 500 rpm or more).

[0070] 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.

[0071] Thereafter, the photoresist film is selectively exposed to light.

[0072] As an example, examples of light that can be used in the exposure process include light having short wavelengths such as activation irradiation conductor i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), as well as light having high energy wavelengths such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0073] More specifically, the exposure light according to an 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).

[0074] In the forming of the photoresist pattern, a negative pattern may be formed.

[0075] The exposed areas of the photoresist film form polymers through crosslinking reactions, such as condensation between organometallic compounds, and therefore have different solubilities from the unexposed areas of the photoresist film.

[0076] Next, the substrate is subjected to a second heat treatment step. The second heat treatment step 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 less soluble in a developer.

[0077] Specifically, the photoresist film corresponding to the unexposed region is dissolved using an organic solvent such as 2-heptanone and then removed, completing the photoresist pattern corresponding to the negative tone image.

[0078] The developer used in the pattern formation method according to an 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 butyrolactone; aromatic compounds such as benzene, xylene, and toluene; or combinations thereof.

[0079] In addition, the method for forming a pattern may further include applying a composition for removing edge beads of a metal-containing resist after the exposure and development processes,

[0080] Specifically, the method may include applying an appropriate amount of the composition for removing edge beads of a metal-containing resist along the edge of a substrate while spinning the substrate at an appropriate speed (e.g., 500 rpm or more).

[0081] As described above, the photoresist pattern 108 formed by exposure to light having a wavelength such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), as well as high-energy light such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam) may have a thickness width of 5 nm to 100 nm. As an example, the photoresist pattern may be formed with a width 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.

[0082] Meanwhile, the photoresist pattern 108 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 linewidth roughness of about 10 nm or less, about 5 nm or less, about 3 nm or less, about 2 nm or less. EXAMPLES

[0083] The present invention will be described in more detail below through examples of the preparation of the composition for removing edge beads of the above-mentioned metal-containing resist. However, the technical features of the present invention are not limited to the following examples.

[0084] Preparation of a composition for removing edge bead of metal-containing resist Example 1 The cyclic compound represented by the following chemical formula A is mixed with propylene glycol methyl ether acetate (PGMEA) as a solvent in the composition shown in Table 1 below, and then the mixture is shaken at room temperature (25°C) to completely dissolve it. The mixture is then passed through a PTFE filter having a pore size of 1 μm to obtain the final composition. [ka]

[0085] Example 2 A composition is obtained in the same manner as in Example 1, except that a cyclic compound represented by the following chemical formula B and methyl isobutyl carbinol (MIBC) are used as a solvent. [ka]

[0086] Comparative Example 1 A composition is obtained in the same manner as in Example 1, except that glycerol is used instead of the compound of formula A.

[0087] Comparative Example 2 A composition was obtained in the same manner as in Example 1, except that acetic acid was used instead of the compound of formula A.

[0088] Comparative Example 3 A composition was obtained in the same manner as in Example 1, except that acetone oxine was used instead of the compound of formula A.

[0089] Comparative Example 4 A composition was obtained in the same manner as in Example 1, except that tetra-n-butylammonium fluoride (TBAF) was used instead of the compound of formula A.

[0090] Preparation Example: Preparation of an Organometallic Photoresist Composition An organometallic compound having the structure of the following formula C was dissolved in 4-methyl-2-pentanol at a concentration of 1 wt %, and then filtered through a 0.1 μm PTFE syringe filter to prepare a photoresist composition. [ka]

[0091] Evaluation: Residual film thickness evaluation (Strip test) and Sn residual amount evaluation before development 1.0 mL of the organometallic compound-containing photoresist composition according to the above Preparation Example was poured onto a 6-inch silicon wafer, left to stand for 20 seconds, and then spin-coated at a speed of 800 rpm for 30 seconds. Then, heat-treated at 180° C. for 60 seconds to obtain a coating film, the thickness of which was measured by ellipsometry. 10 mL of the edge bead removal composition obtained from Example 1, Example 2, and Comparative Example 1 to Comparative Example 4 was poured onto the wafer on which the coating film was formed along the edge, spin-coated for 5 seconds, and dried while rotating at a speed of 1,500 rpm. Then, heat-treated at 150° C. for 60 seconds to obtain a film, the thickness was measured again by ellipsometry to confirm the change in thickness before and after the edge bead removal process, and evaluated according to the following criteria. VPDICP-MS analysis was performed to confirm the amount of Sn remaining, and the results are shown in Table 1. *If the residual thickness is less than 2A: ○, if it is 2A or more: X

[0092] [Table 1]

[0093] Referring to Table 1, it can be seen that the compositions for removing edge beads of metal-containing resist according to Examples 1 and 2 have superior metal removal effects 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.

[0094] Although specific embodiments of the present invention have been described and shown above, the present invention is not limited to the described embodiments, and it is obvious to those skilled in the art that various modifications and variations 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 belong to the scope of the claims of the present invention. [Explanation of symbols]

[0095] 1... Substrate support part 2. Injection nozzle 10. Photoresist solution 12···Edge beads

Claims

1. 50 to 99.99% by weight of an organic solvent; and 0.01 to 50% by weight of a cyclic compound substituted with at least one hydroxy group (—OH) Including, the cyclic compound has 5 to 30 carbon atoms; The cyclic compound has at least one double bond in the ring, 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, dipropylene glycol dimethyl ether, ethanol, 2-butoxyethanol, n-propanol, isopropanol, n-butanol, isobutyl alcohol, hexanol, ethylene glycol, propylene glycol, heptanone, propylene carbonate, carbon dioxide, or the like. butylene diacetate, diethyl ether, dibutyl ether, ethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diisopentyl ether, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, acetonitrile, diacetone alcohol, 3,3-dimethyl-2-butanone, N-methyl-2-pyrrolidone, dimethylacetamide, cyclohexanone methyl-2-hydroxy-2-methylpropionate (HBM), gamma butyrate Lactone (GBL), 1-butanol, ethyl lactate (EL), diethyl butyl ether (DBE), diisopropyl ether (DIAE), acetylacetone, butyl lactate, 4-methyl-2-pentanol (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, ethyl 2-hydroxy-3-methylpropionate.

2. A composition for removing edge bead of a metal-containing resist, the composition being selected from methyl butyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, methyl-2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate, or mixtures thereof.

2. 2. The composition for removing edge beads of a metal-containing resist according to claim 1, wherein the cyclic compound is substituted with one or two hydroxyl groups (-OH).

3. 2. The composition for removing edge beads of a metal-containing resist according to claim 1, wherein the cyclic compound has 5 to 20 carbon atoms.

4. 2. The composition for removing edge beads of a metal-containing resist according to claim 1, wherein the cyclic compound has 5 to 10 carbon atoms.

5. The composition for removing edge beads of a metal-containing resist according to claim 1, wherein the cyclic compound is represented by any one of the following chemical formulas 1 to 3: 【Chemistry 1】 In the above Chemical Formulas 1 to 3, R １ ~R １７ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group; R １ ~R ６ At least one of R ７ ~R １１ At least one of, and R １２ ~R １７ At least one of the groups is a hydroxy group.

6. The composition for removing edge beads of a metal-containing resist according to claim 1, wherein the cyclic compound is one selected from the chemical formulas shown in Group 1 below: 【Chemistry 2】 In Group 1, R １ ~R １７ are each independently hydrogen, a halogen, an amino group, a substituted or unsubstituted C1 to C30 amine group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

7. The composition for removing edge beads of a metal-containing resist according to claim 1, wherein the cyclic compound is one selected from the compounds shown in Group 2 below: 【Chemistry 3】 。

8. 2. The composition for removing edge beads of a metal-containing resist according to claim 1, wherein the metal compound contained in the metal-containing resist contains at least one of an alkyltin oxo group and an alkyltin carboxyl group.

9. The composition for removing edge beads of a metal-containing resist according to claim 1 , wherein the metal compound contained in the metal-containing resist is represented by the following chemical formula 4: 【Chemistry 4】 In the above Chemical Formula 4, R １８ 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 to 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 １９ ~R ２１ Each independently represents -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.

10. applying a metal-containing resist composition onto a substrate; applying a metal-containing resist edge bead removal composition according to any one of claims 1 to 9 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 A pattern forming method comprising:

11. The method of claim 10, further comprising the step of applying a composition for removing edge beads of the metal-containing resist after the step of forming a resist pattern by exposing and developing.

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