Method of forming a pattern

Abstract

The present invention relates to a method of forming a pattern. The method includes: coating a metal-containing resist composition on a substrate, sequentially coating two types of compositions for removing edge beads along the edge of the substrate, performing a heat treatment including drying and heating to form a metal-containing resist film on the substrate, and performing exposure and development on the metal-containing resist film to form a resist pattern; or coating a metal-containing resist composition on a substrate, coating a composition for removing edge beads along the edge of the substrate, performing a heat treatment including drying and heating to form a metal-containing resist film on the substrate, exposing the metal-containing resist film, and developing with a developer composition to form a resist pattern, wherein the details of the two types of compositions for removing edge beads and the developer composition are as described in the specification.

Description

[0001] Citations of relevant applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2022-0010128, filed with the Korean Intellectual Property Office on January 24, 2022, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to a method of forming a pattern, including coating a composition for removing edge beads, and a method of forming a pattern, including coating a composition for removing edge beads and developing to reduce metal contamination occurring along the wafer edge. Background Technology

[0004] In recent years, the semiconductor industry has seen a continuous reduction in critical dimensions. This reduction in dimensions requires new high-performance photoresist materials and patterning methods to meet the needs of processing and patterning increasingly fine features.

[0005] Furthermore, with the rapid development of the semiconductor industry in recent years, there is a demand for semiconductor devices with fast operating speeds and large storage capacities. To meet these requirements, process technologies are being developed to improve the integration, reliability, and response speed of semiconductor devices. In particular, it is crucial to precisely control / implant impurities in the working regions of a silicon substrate and interconnect these regions to form devices and ultra-high-density integrated circuits, which can be achieved through photolithography processes. In other words, it is important to integrate photolithography processes, including coating a photoresist onto the substrate, selectively exposing it to ultraviolet (UV) light (including extreme ultraviolet (UV) light), electron beams, X-rays, etc., and then developing it.

[0006] Specifically, in the process of forming a photoresist layer, the photoresist is mainly applied to the substrate while the silicon substrate is rotated. This application of photoresist to the edges and back surfaces of the substrate can cause indentations or patterning defects in subsequent semiconductor processes such as etching and ion implantation. Therefore, a process called EBR (Edge Bead Removal) is performed to peel off and remove the photoresist coated on the edges and back surfaces of the silicon substrate using a thinner composition. The EBR process requires a composition that exhibits excellent solubility for the photoresist and effectively removes the beads and photoresist residues remaining in the substrate without producing photoresist residues.

[0007] In addition, there is a need to develop photoresist and developer compositions that can ensure excellent etch resistance and resolution in photolithography processes, while improving sensitivity and CD (critical size) uniformity, and also improving LER (line edge roughness) characteristics. Summary of the Invention

[0008] One embodiment provides a method for forming a pattern, including coating a composition for removing edge beads.

[0009] Another embodiment provides a method for forming a pattern, comprising coating a composition for removing edge beads and developing it.

[0010] A method for forming a pattern according to one embodiment includes: coating a metal-containing resist composition onto a substrate; sequentially coating two types of compositions for removing edge beads along the edge of the substrate; performing a heat treatment including drying and heating to form a metal-containing resist film on the substrate; and exposing and developing the metal-containing resist film to form a resist pattern.

[0011] The two types of compositions for removing edge beads can be composition A, which contains a phosphorous compound and an organic solvent; or composition B, which contains a glycol ether or an ester thereof, an ester of a hydroxy acid or an ester of an alkyl ether acid, and an ester of a carboxylic acid.

[0012] Composition A may contain about 0.01 wt% to about 50 wt% of a phosphorous compound and about 50 wt% to about 99.99 wt% of an organic solvent.

[0013] Composition B may contain about 30 wt% to about 75 wt% of a glycol ether or an ester thereof, about 5 wt% to about 50 wt% of an ester of a hydroxy acid or an ester of an alkyl ether acid, and about 15 wt% to about 55 wt% of an ester of a carboxylic acid.

[0014] The coating composition for removing edge beads may include: a first process in which a composition for removing edge beads of either composition A or composition B is coated along the edge of the substrate while the substrate is rotated; and a second process in which a composition for removing edge beads of either composition A or composition B, different from the composition applied in the first process, is coated along the edge of the substrate while the substrate is rotated.

[0015] Following the second process, a third process may be further included, in which a composition for removing edge beads is applied along the edge of the substrate while the substrate is being rotated.

[0016] The composition used in the third process for removing edge beads may be composition C, which may be the same composition used in the first process as in compositions A and B, or may be different from compositions A and B, and may contain acid additives and organic solvents.

[0017] Following the exposure and development processes, the method may further include coating at least one of composition A and composition B.

[0018] Diol ethers or their esters can be one of propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and combinations thereof.

[0019] Esters of hydroxy acids or alkyl ether acids can be ethyl lactate, ethyl 3-ethoxypropionate, or combinations thereof.

[0020] The ester of a carboxylic acid can be methyl 2-hydroxyisobutyrate.

[0021] According to another embodiment, a method for forming a pattern includes: coating a metal-containing resist composition onto a substrate; coating along the edge of the substrate with a composition for removing edge beads; performing a heat treatment process of drying and heating to form a metal-containing resist film on the substrate; exposing the metal-containing resist film; and developing with a developer composition comprising a phosphorous compound and an organic solvent to form a resist pattern.

[0022] The developer composition may contain about 0.01 wt% to about 50 wt% of a phosphorous compound and about 50 wt% to about 99.99 wt% of an organic solvent.

[0023] Phosphorous compounds can be at least one of the following types: 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, methylene diphosphonic acid, nitrilotrimethylene triphosphonic acid, 1H,1H,2H,2H-perfluorooctanephosphonic acid, or combinations thereof.

[0024] The metal-containing resist composition may be a metal compound containing at least one alkyltin oxo group and an alkyltin carboxyl group.

[0025] Metal compounds can be represented by chemical formula 1.

[0026] [Chemical Formula 1]

[0027]

[0028] In chemical formula 1,

[0029] R 1 It is a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, a substituted or unsubstituted C6 or C30 aralkyl, and -R a -ORb (where R) a It is a substituted or unsubstituted C1 to C20 alkylene group, and R b It is one of the C1 to C20 alkyl groups, whether substituted or unsubstituted.

[0030] R 2 To R 4 Each independently is -OR c or -OC(=O)R d ,

[0031] R c It is a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and

[0032] R d It is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or combinations thereof.

[0033] According to one embodiment, the patterning method can reduce metal-based contamination by removing the metal-containing resist coated on the edge and back surface of the substrate, thereby meeting the need for processing and patterning with smaller features.

[0034] According to another embodiment, the patterning method can achieve excellent contrast characteristics by minimizing defects present in the metal-containing resist film and promoting development after the exposure process. Attached Figure Description

[0035] Figure 1 This is a schematic diagram of a photoresist coating device. Detailed Implementation

[0036] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, well-known functions or structures will not be described in order to clarify the present invention.

[0037] For clarity of this disclosure, details irrelevant to the description have been omitted, and throughout this disclosure, identical or similar configuration elements are indicated by the same reference numerals. Furthermore, since the dimensions and thicknesses of each configuration shown in the drawings are arbitrarily illustrated for better understanding and ease of description, the invention is not necessarily limited thereto.

[0038] In the accompanying drawings, the thicknesses of layers, films, panels, regions, etc., are enlarged for clarity. In the accompanying drawings, the thickness of a portion of a layer or region is enlarged for clarity. It will be understood that when an element such as a layer, film, region, or substrate is referred to as being "on" another element, it may be directly on the other element, or there may be an intermediate element present.

[0039] Figure 1 This is a schematic diagram of a photoresist coating device.

[0040] See Figure 1 The substrate support 1 is configured with a substrate W mounted thereon, and the substrate support 1 includes a rotary chuck or a rotary coating machine.

[0041] The substrate support 1 rotates at a predetermined speed in a first direction to provide centrifugal force to the substrate W. The nozzle 2 may be located on the substrate support 1, but is positioned in the atmospheric region away from the upper part of the substrate W, allowing the nozzle to move towards the upper part of the substrate W and spray the photoresist solution 10 during the spraying step. Therefore, the photoresist solution 10 is coated onto the surface of the substrate W by centrifugal force. Here, the photoresist solution 10 supplied to the center of the substrate W is coated while simultaneously spreading to the edges of the substrate W by centrifugal force, with a portion of the photoresist solution 10 moving to the sides of the substrate W and the lower surface of the substrate edges.

[0042] In other words, in the coating process, the photoresist solution 10 is mainly coated by spin coating, wherein a predetermined amount of viscous photoresist solution 10 is supplied to the center of the substrate W, and the photoresist solution 10 gradually diffuses toward the edge of the substrate W by centrifugal force.

[0043] Therefore, the photoresist film is uniformly formed by the rotation speed of the substrate support.

[0044] On the other hand, the rotation causes the solvent to evaporate from the solution, thereby gradually increasing the viscosity. This causes a relatively large amount of photoresist to accumulate on the substrate edge under the action of surface tension, and even severely accumulates on the lower surface of the substrate edge, which is called edge beads 12.

[0045] The following describes a method for forming a pattern according to one embodiment.

[0046] A method for forming a pattern according to one embodiment includes: coating a metal-containing resist composition onto a substrate; sequentially coating two types of compositions for removing edge beads along the edge of the substrate; performing a heat treatment including drying and heating to form a metal-containing resist film on the substrate; and exposing and developing the metal-containing resist film to form a resist pattern.

[0047] A method for forming a pattern according to another embodiment includes: coating a metal-containing resist composition onto a substrate; coating along the edge of the substrate with a composition for removing edge beads; performing a heat treatment including drying and heating to form a metal-containing resist film on the substrate; exposing the metal-containing resist film; and developing with a developer composition comprising a phosphorous compound and an organic solvent to form a resist pattern.

[0048] Specifically, forming a pattern using a metal-containing resist composition may include: coating a substrate on which a thin film is formed by means of spin coating, slot coating, inkjet printing, etc., and drying it to form a resist film. The metal-containing resist composition may contain a tin-based compound, and the tin-based compound may contain at least one of, for example, alkyltin oxogroup and alkyltin carboxyl group.

[0049] For example, a metal compound contained in a metal-containing resist can be represented by chemical formula 1.

[0050] [Chemical Formula 1]

[0051]

[0052] In chemical formula 1,

[0053] R 1 It is a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, a substituted or unsubstituted C6 or C30 aralkyl, and -R a -OR b (where R) a It is a substituted or unsubstituted C1 to C20 alkylene group, and R b It is one of the C1 to C20 alkyl groups, whether substituted or unsubstituted.

[0054] R 2 To R 4 Each independently is -OR c or -OC(=O)R d ,

[0055] R c It is a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and

[0056] R dIt is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or combinations thereof.

[0057] Subsequently, the composition for removing edge beads can be applied.

[0058] In this invention, the method may include sequentially coating two types of compositions for removing edge beads along the edge of a substrate.

[0059] In one embodiment, the two types of compositions for removing edge beads can each independently be composition A, which comprises a phosphorous compound and an organic solvent; or

[0060] Composition B comprises a glycol ether or an ester thereof, an ester of a hydroxy acid or an ester of an alkyl ether acid, and an ester of a carboxylic acid.

[0061] Composition A may contain about 0.01 wt% to about 50 wt% of a phosphorous compound and about 50 wt% to about 99.99 wt% of an organic solvent.

[0062] In one embodiment, composition A may contain a phosphorous compound in an amount of about 0.1 wt% to about 40 wt%, specifically in an amount of about 0.5 wt% to about 30 wt%, or more specifically in an amount of about 1 wt% to about 20 wt%.

[0063] Examples of organic solvents included in composition A according to one embodiment may include, for example, propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), propylene glycol butyl ether (PGBE), ethylene glycol methyl ether, diethyl ethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, ethanol, 2-butoxyethanol, n-propanol, isopropanol, n-butanol, isobutanol, hexanol, ethylene glycol, propylene glycol, heptanone, propylene carbonate, butyl carbonate, diethyl ether, diisopropyl ether, dibutyl ether, acetic acid. Ethyl acetate, ethyl lactate, methyl-2-hydroxyisobutyrate, γ-butyrolactone, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl isobutyl methanol (MIBC), n-butyl acetate, diisopentyl ether, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, acetonitrile, acetylacetone, diacetone alcohol, 3,3-dimethyl-2-butanone, N-methyl-2-pyrrolidone, dimethylacetamide, cyclohexanone, or mixtures thereof, but not limited thereto.

[0064] For example, phosphorous compounds can be at least one type 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, methylene diphosphonic acid, nitrilotrimethylene triphosphonic acid, 1H,1H,2H,2H-perfluorooctanephosphonic acid, or combinations thereof.

[0065] Composition B may contain about 30 wt% to about 75 wt% of a glycol ether or an ester thereof, about 5 wt% to about 50 wt% of an ester of a hydroxy acid or an ester of an alkyl ether acid, and about 15 wt% to about 55 wt% of an ester of a carboxylic acid.

[0066] In one specific embodiment, composition B may contain glycol ethers or esters thereof in an amount of about 35 wt% to about 70 wt%, specifically in an amount of about 40 wt% to about 65 wt%, or more specifically in an amount of about 45 wt% to about 60 wt%.

[0067] In one embodiment, composition B may contain esters of hydroxy acids or esters of alkyl ether acids in an amount of about 5 wt% to about 45 wt%, specifically in an amount of about 5 wt% to about 40 wt%, or more specifically in an amount of about 10 wt% to about 40 wt%.

[0068] In one embodiment, composition B may contain an ester of carboxylic acid in an amount of about 15 wt% to about 50 wt%, specifically in an amount of about 20 wt% to about 45 wt%, or more specifically in an amount of about 25 wt% to about 40 wt%.

[0069] For example, a glycol ether or its ester can be one of propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and combinations thereof.

[0070] For example, esters of hydroxy acids or esters of alkyl ether acids can be a type of ethyl lactate, ethyl 3-ethoxypropionate, and combinations thereof.

[0071] For example, an ester of a carboxylic acid can be methyl 2-hydroxyisobutyrate.

[0072] The patterning method according to the invention, which includes edge bead removal, can be used particularly effectively to remove metal-containing resists, and specifically, to remove unwanted metal residues, such as tin-based metal residues.

[0073] In this invention, the coating composition for removing edge beads can be repeated several times to reduce metal-based contamination on the edges and back surfaces of the substrate, and also to reduce the resist to a desired level.

[0074] For example, at least two types of compositions for removing edge beads can be applied. Furthermore, the same composition for removing edge beads can be applied several times.

[0075] In one specific embodiment, when at least two types of compositions for removing edge beads are applied, the coating of these compositions can be performed sequentially.

[0076] For example, one type of composition for removing edge beads can be applied, and then another type of composition for removing edge beads can be applied.

[0077] For example, applying a composition for removing edge beads may include: step 1, applying an appropriate amount of either composition A or composition B as a composition for removing edge beads along the edge of a substrate at an appropriate speed (e.g., about 500 rpm or higher, specifically about 500 rpm or higher and about 3000 rpm or lower) while rotating the substrate; and step 2, applying an appropriate amount of another composition for removing edge beads at an appropriate speed (e.g., about 500 rpm or higher, specifically about 500 rpm or higher and about 3000 rpm or lower), the other composition being a different composition from composition A and composition B than the one applied in step 1.

[0078] Following step 2, the process may further include step 3, applying the composition for removing edge beads at an appropriate speed (e.g., about 500 rpm or higher, specifically about 500 rpm or higher and about 3000 rpm or lower) while rotating the substrate.

[0079] For example, in step 3, the same composition for removing edge beads as the composition applied in step 1 can be applied to compositions A and B in appropriate amounts.

[0080] For example, in step 3, composition C, which contains acid additives and organic solvents, can be applied in an appropriate amount as a composition for removing edge beads, different from compositions A and B.

[0081] The acid additives and organic solvents included in composition C can be any materials known in the art suitable for compositions used to remove edge beads, without limitation.

[0082] Subsequently, a first heat treatment process can be performed on 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 160°C, which can evaporate the solvent and make the photoresist film adhere more firmly to the substrate.

[0083] Then, an exposure process for selectively exposing the photoresist film can be performed.

[0084] Examples of light used in exposure processes can include not only light with short wavelengths, such as i-line (wavelength: 365nm), KrF excimer laser (wavelength: 248nm), and ArF excimer laser (wavelength: 193nm), but also light with high-energy wavelengths, such as EUV (extreme ultraviolet; wavelength: 13.5nm) and E-Beam (electron beam).

[0085] Specifically, the light used for exposure according to one embodiment can be light with a short wavelength in the range of about 5 nm to about 150 nm, but it can also be light with a high-energy wavelength, such as EUV (extreme ultraviolet; wavelength: about 13.5 nm), E-Beam (electron beam), etc.

[0086] When forming a photoresist pattern, a negative pattern can be formed.

[0087] The exposed areas of a photoresist film have different solubility than the unexposed areas because the polymer is formed through cross-linking reactions (such as condensation between organometallic compounds).

[0088] Subsequently, the substrate can undergo a second heat treatment. This second heat treatment process can be performed at approximately 90°C to approximately 200°C. This second heat treatment process allows less of the exposed areas of the photoresist film to dissolve in the developer.

[0089] Subsequently, development can be performed using a developer composition.

[0090] Specifically, a photoresist pattern corresponding to a negative-toned image is completed by dissolving and removing the photoresist film corresponding to the unexposed areas using a developer composition.

[0091] The developing composition used in the method for forming a pattern can be, for example, an organic solvent, such as ketones (e.g., methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, etc.), alcohols (e.g., 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, methanol, propylene glycol methyl ether (PGME), methyl isobutyl methanol (MIBC), etc.), esters (e.g., propylene glycol methyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, methyl 2-hydroxyisobutyrate, butyrolactone, etc.), aromatic compounds (e.g., benzene, xylene, toluene, etc.) or combinations thereof.

[0092] The developer composition according to one embodiment of the present invention may contain a phosphorous compound and an organic solvent, and may be, for example, composition A described above.

[0093] The developer composition may contain about 0.01 wt% to about 50 wt% of a phosphorous compound and about 50 wt% to about 99.99 wt% of an organic solvent.

[0094] In one specific embodiment, the developer composition may contain a phosphorous compound in an amount of about 0.1 wt% to about 40 wt%, specifically in an amount of about 0.5 wt% to about 30 wt%, or more specifically in an amount of about 1 wt% to about 20 wt%.

[0095] Specific examples of phosphites and organic solvents contained in the developer composition are the same as those in composition A above.

[0096] After the exposure and development processes, a process of coating at least one of composition A and composition B can be additionally performed to minimize the amount of residual metal that may be present at the edges of the substrate.

[0097] As described above, photoresist patterns formed by exposure to high-energy light (such as EUV (extreme ultraviolet; wavelength: approximately 13.5 nm), E-Beam (electron beam), etc.) and short-wavelength light (such as i-line (wavelength: approximately 365 nm), KrF stimulated excimer laser (wavelength: approximately 248 nm), ArF stimulated excimer laser (wavelength: approximately 193 nm), etc.) can have widths ranging from approximately 5 nm to approximately 100 nm. For example, photoresist patterns can have widths ranging from approximately 5 nm to approximately 90 nm, approximately 5 nm to approximately 80 nm, approximately 5 nm to approximately 70 nm, approximately 5 nm to approximately 60 nm, approximately 5 nm to approximately 50 nm, approximately 5 nm to approximately 40 nm, approximately 5 nm to approximately 30 nm, or approximately 5 nm to approximately 20 nm.

[0098] On the other hand, the photoresist pattern can have a half pitch of less than or equal to about 50 nm (e.g., less than or equal to about 40 nm, for example, less than or equal to about 30 nm, for example, less than or equal to about 20 nm, for example, less than or equal to about 15 nm) and a pitch of less than or equal to about 10 nm, less than or equal to about 5 nm, less than or equal to about 3 nm or less than or equal to about 2 nm.

[0099] In the following description, the invention will be described in more detail through examples relating to the preparation of compositions and / or developer compositions for removing the edge beads of the aforementioned metal-containing resist. However, the technical features of the invention are not limited to the following examples.

[0100] Preparation Examples 1 to 6: Preparation of Composition A

[0101] A phosphorous compound was mixed with an organic solvent to have each of the compositions shown in Table 1, and then completely dissolved therein by shaking at room temperature (25°C). Subsequently, the solution was passed through a filter having a pore size of 1 μm and being made of PTFE (polytetrafluoroethylene) material to obtain composition A.

[0102] (Table 1)

[0103]

[0104] Preparation Example 7: Preparation of Composition B

[0105] 50 wt% propylene glycol methyl ether acetate (PGMEA), 10 wt% ethyl lactate, and 40 wt% methyl 2-hydroxyisobutyrate were mixed and completely dissolved by shaking at room temperature (25°C). The solution was then passed through a filter with a 1 μm pore size made of PTFE material to obtain composition B.

[0106] Preparation Example 8: Preparation of Composition C

[0107] 10 wt% of glycolic acid compound and 90 wt% of PGMEA / PGME were mixed [mixing ratio = 5:5] and then completely dissolved by shaking at room temperature (25°C). Subsequently, the solution was passed through a filter with a pore size of 1 μm and formed of PTFE material to obtain composition C.

[0108] Preparation Example 9: Preparation of a photoresist composition containing organometallic compounds

[0109] An organometallic compound with the chemical 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 obtain a photoresist composition.

[0110] [Chemical formula C]

[0111]

[0112] Evaluation 1: Residual Tin (Sn) Content

[0113] 1.0 mL of the organometallic photoresist composition according to Preparation Example 9 was cast onto a 4-inch silicon wafer, allowed to stand for 20 seconds, and then spin-coated at 1500 rpm for 30 seconds. While rotating the wafer with the photoresist film at 800 rpm, 6.5 mL of each of the compositions according to Preparation Examples 1 to 8 for removing edge beads was sequentially placed along the edge of the wafer with the compositions shown in Table 2, then spin-coated for 3 seconds, and dried for 25 seconds while rotating the wafer at 1500 rpm. VPD ICP-MS analysis was then performed to check the Sn content.

[0114] (Table 2)

[0115]

[0116]

[0117] Referring to Table 2, the results show that, compared with the method of forming a pattern by coating the composition for removing edge beads according to Comparative Examples 1 to 6, the method of forming a pattern by coating the composition for removing edge beads according to Examples 1 to 12 has a superior metal removal effect, thereby further promoting the reduction of residual metal.

[0118] Evaluation 2: Contrast performance

[0119] The prepared photoresist (PR) composition containing organometallic material was spin-coated onto an 8-inch wafer at 1,500 rpm for 30 seconds, and then heat-treated at 100°C for 60 seconds to prepare the coated wafer.

[0120] The patterned wafer was patterned by exposing the coated wafer to light at 20 mJ to 60 mJ using a KrF scanner (PAS 5500 / 700D, ASML) to form a rectangular pattern of 1.2 cm × 0.9 cm. It was then heat-treated at 180 °C for 60 seconds and developed by coating with composition A according to the preparation example as the developing solution. Finally, it was heat-treated at 150 °C for 60 seconds to complete the patterning process.

[0121] The thickness of the patterned wafer with respect to each exposure area was measured to obtain a contrast curve used to calculate the contrast performance (γ(contrast)), and the results are shown in Table 3.

[0122] (Table 3)

[0123] Example 13 Preparation Example 2 37 Example 14 Preparation Example 3 44 Example 15 Preparation Example 4 40 Comparative Example 7 Preparation Example 7 22 Comparative Example 8 Preparation Example 8 25

[0124] Referring to Table 3, when composition A containing phosphorous compounds is used as the developer for a photoresist film containing organometallic compounds, superior contrast is achieved compared to when composition A is not used.

[0125] Some embodiments of the present invention have been described and illustrated above. However, it will be apparent to those skilled in the art that the present invention is not limited to the described embodiments, and various modifications and variations can be made without departing from the spirit and scope of the invention. Therefore, such modifications or variations should not be understood in isolation from the technical concept and aspects of the present invention, and the modified embodiments are within the scope of the claims of the present invention.

[0126] <Explanation of Figure Markers>

[0127] 1. Substrate support

[0128] 2 nozzles

[0129] 10 Photoresist Solution

[0130] 12 edge beads.

Claims

1. A method for forming a pattern, comprising: A metal-containing photoresist composition is coated onto a substrate; Two types of compositions for removing edge beads are sequentially coated along the edge of the substrate; A heat treatment including drying and heating is performed to form a metal-containing resist film on the substrate; as well as The metal-containing resist film is exposed and developed to form a resist pattern. The two types of compositions for removing edge beads are each independently... Composition A, comprising a phosphorous compound and an organic solvent; or Composition B comprises a glycol ether or an ester thereof, an ester of a hydroxy acid or an ester of an alkyl ether acid, and an ester of a carboxylic acid. The sequential coating of two types of compositions for removing edge beads includes: The first process involves coating along the edge of the substrate a composition for removing edge beads, which is either composition A or composition B, while simultaneously rotating the substrate. The second process involves coating along the edge of the substrate with a composition for removing edge beads, which is a different composition from that used in the first step, consisting of composition A and composition B, while rotating the substrate.

2. The method according to claim 1, wherein Composition A comprises 0.01 wt% to 50 wt% of the phosphorous compound and 50 wt% to 99.99 wt% of the organic solvent.

3. The method according to claim 1, wherein Composition B comprises 30 wt% to 75 wt% of the glycol ether or its ester, 5 wt% to 50 wt% of the ester of the hydroxy acid or the ester of the alkyl ether acid, and 15 wt% to 55 wt% of the ester of the carboxylic acid.

4. The method according to claim 1, wherein Following the second process, the method further includes: The third process involves coating along the edge of the substrate with a composition for removing edge beads, which is the same composition as that used in the first process, or different from compositions A and B, while rotating the substrate.

5. The method according to claim 4, wherein The composition for removing edge beads, which differs from compositions A and B, contains acid additives and organic solvents.

6. The method according to claim 1, wherein Following the exposure and development processes, the method further includes coating at least one of composition A and composition B.

7. The method according to claim 1, wherein The glycol ether or its ester is one of propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and combinations thereof. The ester of the hydroxy acid or the ester of the alkyl ether acid is one of ethyl lactate, ethyl 3-ethoxypropionate, and combinations thereof, and The ester of the carboxylic acid is methyl 2-hydroxyisobutyrate.

8. A method for forming a pattern, comprising: A metal-containing photoresist composition is coated onto a substrate; A composition for removing edge beads is applied along the edge of the substrate; A heat treatment including drying and heating is performed to form a metal-containing resist film on the substrate; The metal-containing resist film is exposed to light; as well as Developing is performed using a developer composition containing phosphite compounds and organic solvents to form a resist pattern.

9. The method according to claim 8, wherein The developer composition comprises 0.01 wt% to 50 wt% of the phosphite compound and 50 wt% to 99.99 wt% of the organic solvent.

10. The method according to claim 1 or 8, wherein The phosphorous compound is at least one of the following types: 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, methylene diphosphonic acid, triazinetrimethylene triphosphonic acid, 1H,1H,2H,2H-perfluorooctanephosphonic acid, or combinations thereof.

11. The method according to claim 1 or 8, wherein The metal-containing resist composition comprises a metal compound containing at least one of alkyltin oxo group and alkyltin carboxyl group.

12. The method according to claim 11, wherein, The metal compound is represented by chemical formula 1: [Chemical Formula 1] In chemical formula 1, R 1 It is a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, a substituted or unsubstituted C6 or C30 aralkyl, and -R a -OR b One of them, where R a It is a substituted or unsubstituted C1 to C20 alkylene group and R b It is a substituted or unsubstituted C1 to C20 alkyl group. R 2 To R 4 Each independently is -OR c or -OC(=O)R d R c It is a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and R d It is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or combinations thereof.

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