Composition for removing edge beads of metal-containing resists or developer composition for metal-containing resists, and pattern forming method using the same

Abstract

To provide a composition for removing edge beads of metal-containing resists or a developer composition for metal-containing resists, and to provide a pattern forming method using the composition.SOLUTION: The composition for removing edge beads of metal-containing resists or the developer composition for metal-containing resists contains: a C1-C10 carboxylic acid compound substituted with at least one fluorine atom; and an organic solvent. The pattern forming method uses the composition.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] This description relates to a composition for removing edge bead of a metal-containing resist or a developer composition for a metal-containing resist, and a patterning method utilizing the same. [Background technology]

[0002] Recently, the semiconductor industry has been accompanied by a continuing shrinkage of critical dimensions which has required a new class of high performance photoresist materials and patterning methods to meet the demands of fabricating and patterning smaller and smaller features.

[0003] Recently, the rapid development of the semiconductor industry has led to the demand for faster operation speeds and larger storage capacity for semiconductor devices, and process technologies have been developed to keep pace with these demands and 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 a silicon substrate so that these regions are interconnected to form elements and ultra-high density integrated circuits, which can be achieved through photolithography. In other words, it has become important to consider the integration of the photolithography process, which involves coating a photoresist on a substrate, selectively exposing it to ultraviolet light (including extreme ultraviolet light), electron beams, or X-rays, and then developing it.

[0004] In particular, in the process of forming a photoresist layer, 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 squeezing or pattern defects in semiconductor post-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, that is, an edge bead removal (EBR) process, is performed. The EBR process requires a composition that has excellent solubility in photoresist and effectively removes beads and photoresist remaining on the substrate without leaving any resist residue.

[0005] In addition, there is a need to develop a photoresist that can guarantee excellent etching resistance and resolution in the photolithography process while improving sensitivity and CD (critical dimension) uniformity and improving LER (line edge roughness) characteristics, as well as a developer composition that can achieve this. Summary of the Invention [Problem to be solved by the invention]

[0006] One embodiment provides a metal-containing resist edge bead removal composition or a metal-containing resist developer composition.

[0007] Another embodiment provides a method of forming a pattern using the composition. [Means for solving the problem]

[0008] A composition for removing edge bead of a metal-containing resist or a developer composition for a metal-containing resist according to one embodiment includes at least one fluorine-substituted C1-C10 carboxylic acid compound; and an organic solvent.

[0009] A method of forming a pattern according to another embodiment includes the steps of applying a metal-containing resist composition onto a substrate, applying the metal-containing resist edge bead removal composition along an edge of the substrate, a heat treatment step of drying and heating to form a metal-containing resist film on the substrate, exposing the metal-containing photoresist film to light, and developing.

[0010] In still another embodiment, a method for forming a pattern includes the steps of applying a metal-containing resist composition onto a substrate, removing an edge bead of the metal-containing resist, drying and heating to form a metal-containing resist film on the substrate, exposing the metal-containing photoresist film to light, and developing the metal-containing resist using a developer composition.

[0011] In still another embodiment, a method of forming a pattern includes applying the above-described metal-containing resist edge bead removal composition along an edge of the substrate, a heat treatment step of drying and heating to form a metal-containing resist film on the substrate, exposing the metal-containing photoresist film to light, and developing using the above-described metal-containing resist developer composition. Effect of the Invention

[0012] The edge bead removal composition for metal-containing resist according to one embodiment can meet the demands of smaller feature processing and patterning by reducing metal-based contamination inherent in metal-containing resist and removing resist applied to the edge and backside of a substrate.

[0013] According to another embodiment, the metal-containing developer composition minimizes defects present in a metal-containing photoresist film after an exposure process and facilitates development, thereby enabling excellent contrast characteristics, excellent sensitivity, and reduced line edge roughness (LER). [Brief description of the drawings]

[0014] [Figure 1] FIG. 1 is a schematic diagram showing a photoresist coating apparatus. [Diagram 2] 1A to 1C are cross-sectional views illustrating a process sequence for explaining a pattern forming method. [Diagram 3] 1A to 1C are cross-sectional views illustrating a process sequence for explaining a pattern forming method. [Figure 4] 1A to 1C are cross-sectional views illustrating a process sequence for explaining a pattern forming method. [Diagram 5] This is a contrast curve obtained by measuring the thickness of each exposed portion of a patterned wafer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the preferred 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 known functions or configurations will be omitted in order to clarify the gist of the description.

[0016] In order to clearly explain the present description, parts unnecessary for the description are omitted, and the same or similar components are designated by the same reference numerals throughout the specification. Furthermore, the size and thickness of each component shown in the drawings are arbitrarily shown for the convenience of explanation, and the present description is not necessarily limited to those shown in the drawings.

[0017] In the drawings, the thickness of a plurality of layers and regions is exaggerated to clearly show the layers and regions. Also, in the drawings, the thickness of some layers and regions is exaggerated for the convenience of explanation. When a layer, film, region, plate, or other part is said to be "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 therebetween.

[0018] In this description, "substituted" means that the hydrogen atom is replaced with deuterium, a halogen group, a hydroxy group, a thiol group, a cyano group, a carbonyl 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 C1-C20 sulfide group. "Unsubstituted" means that the hydrogen atom remains as a hydrogen atom without being replaced with another substituent.

[0019] In this description, unless otherwise specified, the term "alkyl group" refers to a straight or branched chain aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0020] The alkyl group may be 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-C5 alkyl group means an alkyl group containing 1-5 carbon atoms in the alkyl chain, and is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0021] 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 tert-butyl group, a pentyl group, and a hexyl group.

[0022] In the formulae depicted herein, t-Bu refers to a tert-butyl group.

[0023] In this description, unless otherwise defined, a "cycloalkyl group" refers to a monovalent cyclic aliphatic hydrocarbon group.

[0024] The cycloalkyl group can be a C3-C10 cycloalkyl group, such as a C3-C8 cycloalkyl group, a C3-C7 cycloalkyl group, or a C3-C6 cycloalkyl group. For example, the cycloalkyl group can be, but is not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

[0025] In this description, unless otherwise defined, a "heterocycloalkyl group" means a cycloalkyl group containing at least one heteroatom selected from the group consisting of N, O, S, P and Si.

[0026] In this description, unless otherwise defined, an "alkenyl group" refers to an aliphatic unsaturated alkenyl group which is a straight-chain or branched-chain aliphatic hydrocarbon group and contains one or more double bonds.

[0027] In this description, unless otherwise defined, an "alkynyl group" refers to an aliphatic unsaturated alkynyl group which is a straight-chain or branched-chain aliphatic hydrocarbon group and contains one or more triple bonds.

[0028] As used herein, the term "aryl group" refers to a substituent in which all elements of the cyclic group have p-orbitals and these p-orbitals form conjugation, including monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of carbon atoms) functional groups.

[0029] In this description, the term "heteroaryl group" refers to an aryl group containing at least one heteroatom selected from the group consisting of N, O, S, P and Si. Two or more heteroaryl groups may be directly linked through a sigma bond, or when the heteroaryl group contains two or more rings, the two or more rings may be fused together. When the heteroaryl group is a fused ring, each ring may contain 1 to 3 of the heteroatoms.

[0030] More specifically, the substituted or unsubstituted C6 to C30 aryl group may be, but is not limited to, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted 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.

[0031] More specifically, the substituted or unsubstituted C2-C30 heterocyclic group is a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted phenyl ... or unsubstituted isoquinolinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted benzonaphthofuranyl, substituted or unsubstituted benzonaphthothiophenyl, substituted or unsubstituted benzofuranofluorenyl, substituted or unsubstituted benzothiophenefluorenyl, or combinations thereof.

[0032] FIG. 1 is a schematic diagram showing a photoresist coating apparatus.

[0033] Referring to FIG. 1, a substrate support 1 on which a substrate W is placed is provided. The substrate support 1 may include a spin chuck or a spin coater.

[0034] The substrate support 1 rotates at a predetermined rotation speed in a first direction to provide centrifugal force to the substrate W. A spray nozzle 2 is located on the substrate support 1, and the spray nozzle 2 is located in an atmospheric region away from the top of the substrate W and moves to the top of the substrate during the solution supply step to spray the photoresist solution 10. Thus, 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 and applied to the periphery of the substrate W by the centrifugal force, and some of it moves to the side of the substrate and the underside of the periphery of the substrate.

[0035] That is, in the coating process, the photoresist solution 10 is mainly coated by spin coating, and a predetermined amount of viscous photoresist solution 10 is supplied to the center of the substrate W and gradually spreads toward the periphery of the substrate by centrifugal force.

[0036] Therefore, the thickness of the photoresist is formed evenly depending on the rotation speed of the substrate support.

[0037] However, as the solvent evaporates and the viscosity gradually increases, a relatively large amount of photoresist accumulates around the edge of the substrate due to surface tension, and more seriously, the photoresist accumulates on the underside of the edge of the substrate, which is called an edge bead 12.

[0038] Hereinafter, a composition for removing edge bead of a metal-containing resist or a developer composition for a metal-containing resist according to one embodiment will be described.

[0039] A composition for removing edge bead of a metal-containing resist or a developer composition for a metal-containing resist according to one embodiment of the present invention comprises at least one fluorine-substituted C1-C10 carboxylic acid compound; and an organic solvent.

[0040] The C1-C10 carboxylic acid compound having at least one fluorine atom substituted therewith can promote the reaction with the photoresist of the exposed portion, thereby increasing the solubility difference with the non-exposed portion.

[0041] In addition, by containing fluorine, which is an electron-withdrawing group, it is possible to maintain a pKa suitable for improving sensitivity and resolution, which is advantageous for realizing fine patterns and controlling scum.

[0042] For example, the C1 to C10 carboxylic acid compound substituted with at least one fluorine atom may be represented by the following Chemical Formula 1. [ka] In the above Chemical Formula 1, R 1 ~R 3 each independently represents hydrogen, fluorine, a fluorine-containing group, or a substituted or unsubstituted C1-C5 alkyl group, n is an integer from 1 to 5; R 1 ~R 3 At least one of is fluorine or a fluorine-containing group.

[0043] For example, the above R 2 and the above R 3 At least one of may be fluorine or a fluorine-containing group.

[0044] For example, the above R 2 and the above R 3 may each independently be fluorine or a fluorine-containing group.

[0045] For example, the above R 2 and the above R 3 may each independently be fluorine.

[0046] As an example, the C1-C10 carboxylic acid compound substituted with at least one fluorine atom may be at least one of difluoroacetic acid, 2,2-difluoropropionic acid, trifluoroacetic acid, and monofluoroacetic acid.

[0047] In one embodiment, the composition for removing edge bead of a metal-containing resist or the developer composition for a metal-containing resist may contain 0.01 to 5 wt % of the at least one fluorine-substituted C1 to C10 carboxylic acid compound based on the total amount of the composition, and 95 to 99.99 wt % of an organic solvent based on the total amount of the composition.

[0048] In a specific embodiment, the composition for removing edge bead of a metal-containing resist or the developer composition for a metal-containing resist may contain 0.05 to 5 wt %, specifically 0.05 to 1 wt %, more specifically 0.05 to 0.5 wt % of at least one fluorine-substituted C1 to C10 carboxylic acid compound, based on the total amount of the composition.

[0049] Examples of organic solvents contained in the composition for edge bead removal of metal-containing resist or the developer composition according to one embodiment include propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), propylene glycol butyl ether (PGBE), ethylene glycol methyl ether, diethyl glycol ethyl methyl ether, dipropyl glycol dimethyl ether, ethanol, 2-butoxyethanol, n-propanol, isopropanol, n-butanol, isobutyl alcohol, hexanol, ethylene glycol, propylene glycol, heptanone, propylene carbonate, butylene carbonate, diethyl ether, dibutyl ether, ethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diisopentyl ether, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, acetonitrile, diacetone alcohol, 3,3-Dimethyl-2-butanone, N-methyl-2-pyrrolidone, dimethylacetamide, cyclohexanone, methyl-2-hydroxy-2-methylpropanoate (HBM), gamma-butyrolactone (GBL), 1-butanol (n-Butanol), ethyl lactate (EL), diene 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, cyclopentanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, methyl 2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate, or mixtures thereof.

[0050] Metal-containing resist edge bead removal compositions according to the present invention can be particularly effective in removing metal-containing resists, and more specifically, undesirable metal residues, such as tin-based metal residues.

[0051] In addition, the developer composition for a metal-containing resist according to the present invention minimizes defects present in a metal-containing photoresist film after an exposure process and facilitates development, thereby achieving excellent pattern characteristics.

[0052] Not only that, excellent sensitivity and reduced line edge roughness (LER) can also be achieved.

[0053] In the case where other additives described later are included, the organic solvent may be included in an amount remaining after excluding the components included therein.

[0054] The composition may further include at least one other additive selected from the group consisting of a surfactant, a dispersant, a moisture absorbent, and a coupling agent.

[0055] The surfactant may improve the coating uniformity and wetting of the photoresist composition. In an exemplary embodiment, the surfactant may be, but is not limited to, a sulfate salt, a sulfonate salt, a phosphate salt, a soap, an amine salt, a quaternary ammonium salt, a polyethylene glycol, an alkylphenol ethylene oxide adduct, a polyhydric alcohol, a nitrogen-containing vinyl polymer, or a combination thereof. For example, the surfactant may include an alkylbenzene sulfonate salt, an alkylpyridinium salt, a polyethylene glycol, or a quaternary ammonium salt. When the photoresist composition includes the surfactant, the surfactant may be included in an amount of about 0.001% by weight to about 3% by weight based on the total weight of the photoresist composition.

[0056] The dispersant may serve to uniformly disperse each component of the photoresist composition in the photoresist composition. In an exemplary embodiment, the dispersant may be, but is not limited to, an epoxy resin, polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, glucose, sodium dodecyl sulfate, sodium citrate, oleic acid, linoleic acid, or a combination thereof. When the photoresist composition includes the dispersant, the dispersant may be included in an amount of about 0.001 wt % to about 5 wt % based on the total weight of the photoresist composition.

[0057] The moisture absorbent may prevent adverse effects of moisture on the photoresist composition. For example, the moisture absorbent may prevent metals contained in the photoresist composition from being oxidized by moisture. In an exemplary embodiment, the moisture absorbent may be, but is not limited to, polyoxyethylenenonylphenolether, polyethylene glycol, polypropylene glycol, polyacrylamide, or a combination thereof. When the photoresist composition includes the moisture absorbent, the moisture absorbent may be included in an amount of about 0.001 wt % to about 10 wt % based on the total weight of the photoresist composition.

[0058] The coupling agent may improve adhesion to an underlying film when the photoresist composition is coated on the underlying film. In an exemplary embodiment, the coupling agent may include a silane coupling agent. The silane coupling agent may be, but is not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, or trimethoxy[3-(phenylamino)propyl]silane. When the photoresist composition includes the coupling agent, the coupling agent may be included in an amount of about 0.001% by weight to about 5% by weight based on the total weight of the photoresist composition.

[0059] The metal 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.

[0060] For example, the metal compound contained in the metal-containing resist may be represented by the following Chemical Formula 2: [ka] In the above Chemical Formula 2, R 4 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 C7 to C30 arylalkyl group, and L a -OR a (Here, L a is a substituted or unsubstituted C1 to C20 alkylene group, R a is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group; R 5 ~R 7 are each independently a halogen, 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 C7 to C30 arylalkyl group, alkoxo and aryloxo (-OR b , where R b 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), a carboxyl group (-O(CO)R 6 , R 6is 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), alkylamide or dialkylamide (-NR 7 R 8 , where R 7 and R 8 are each independently a hydrogen atom, 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), an amidate (-NR 9 (COR 10 ), where R 9 and R 10 are each independently a hydrogen atom, 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), or an amidinate (-NR 11 C(NR 12 )R 13 , where R 11 , R 12 and R 13 are each independently a hydrogen atom, 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; At least one of R5 to R7 is an alkoxy or aryloxy group (-OR b , where R bis 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), a carboxyl group (-O(CO)R 6 , R 6 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), alkylamide or dialkylamide (-NR 7 R 8 , where R 7 and R 8 are each independently a hydrogen atom, 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), an amidate (-NR 9 (COR 10 ), where R 9 and R 10 are each independently a hydrogen atom, 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), or an amidinate (-NR 11 C(NR 12 )R 13 , where R 11 , R 12 and R 13are each independently a hydrogen atom, 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.

[0061] For example, the metal 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.

[0062] Meanwhile, according to another embodiment, there may be provided a method for forming a pattern, comprising removing an edge bead using the above-mentioned composition for removing edge bead of a metal-containing resist. For example, the manufactured pattern may be a photoresist pattern. More specifically, it may be a negative type photoresist pattern.

[0063] A method for forming a pattern according to one embodiment includes the steps of applying a metal-containing resist composition onto a substrate, applying the metal-containing resist edge bead removal composition along an edge of the substrate, a heat treatment step of drying and heating to form a metal-containing resist film on the substrate, exposing the metal-containing photoresist film to light, and developing.

[0064] 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 organic oxy group-containing tin compound and an organic carbonyloxy group-containing tin compound.

[0065] More specifically, the method may include applying an appropriate amount of the composition for removing edge bead 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).

[0066] Next, a first heat treatment process is performed to heat the substrate on which the photoresist film is formed. The first heat treatment process may be performed at a temperature of about 80° C. to about 120° C., during which the solvent is evaporated and the photoresist film may be more firmly attached to the substrate.

[0067] Then, the photoresist film is selectively exposed to light.

[0068] As an example, examples of light that can be used in the exposure process include light having short wavelengths such as activation radiation i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), as well as light having high energy wavelengths such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0069] More specifically, the exposure light according to an embodiment may be short-wavelength light having a wavelength range of 5 nm to 150 nm, and may be light having a high-energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0070] In the forming of the photoresist pattern, a negative type pattern may be formed.

[0071] The exposed area of ​​the photoresist film forms a polymer through a crosslinking reaction, such as condensation between organometallic compounds, and thus has a different solubility from the unexposed area of ​​the photoresist film.

[0072] Next, a second heat treatment step is performed on the substrate. 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 difficult to dissolve in a developer.

[0073] Specifically, the photoresist film corresponding to the unexposed area is dissolved using an organic solvent such as 2-heptanone and then removed, thereby completing the photoresist pattern corresponding to the negative tone image.

[0074] The developer used in the pattern formation method according to one embodiment may be an organic solvent, examples of which 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.

[0075] As described above, the photoresist pattern 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 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.

[0076] Meanwhile, the photoresist pattern may have a half-pitch of about 50 nm or less, e.g., 40 nm or less, e.g., 30 nm or less, e.g., 20 nm or less, e.g., 15 nm or less, and a line width roughness of about 10 nm or less, about 5 nm or less, about 3 nm or less, about 2 nm or less.

[0077] According to another embodiment, a method for forming a pattern includes applying a metal-containing resist composition onto a substrate, removing edge beads of the metal-containing resist, drying and heating to form a metal-containing resist film on the substrate, exposing the metal-containing photoresist film to light, and developing the metal-containing resist using a developer composition.

[0078] The step of applying a metal-containing resist composition onto a substrate is as described above.

[0079] The edge bead removal step of the metal-containing resist can be carried out by applying an appropriate amount of a commonly known organic solvent or composition for edge bead removal along the edge of the substrate while spinning the substrate at an appropriate speed (e.g., 500 rpm or more).

[0080] The heat treatment step of drying and heating to form a metal-containing resist film on the substrate is as described above.

[0081] The step of exposing the metal-containing photoresist film is as described above.

[0082] The photoresist film corresponding to the unexposed area is dissolved and then removed using the developer composition for the metal-containing resist, thereby completing the photoresist pattern corresponding to the negative tone image.

[0083] The method of forming a pattern by development will be specifically described below with reference to the drawings.

[0084] 2 to 4 are cross-sectional views showing the process sequence for explaining the pattern formation method.

[0085] Referring to FIG. 2, the exposed photoresist film is developed to form a photoresist pattern 130P.

[0086] In an exemplary embodiment, the exposed photoresist film may be developed to remove the unexposed areas of the photoresist film to form a photoresist pattern 130P consisting of the exposed areas of the photoresist film. The photoresist pattern 130P may include a plurality of openings OP.

[0087] In an exemplary embodiment, the photoresist film may be developed by a negative-tone development (NTD) process, in which a metal-containing photoresist developer composition according to an embodiment may be used as a developer composition.

[0088] Referring to FIG. 3, the feature layer 110 is processed using the photoresist pattern 130P from the result of FIG.

[0089] For example, in order to process the feature layer 110, various processes may be performed, such as a process of etching the feature layer 110 exposed through the openings OP of the photoresist pattern 130P, a process of implanting impurity ions into the feature layer 110, a process of forming an additional film on the feature layer 110 through the openings OP, a process of deforming a part of the feature layer 110 through the openings OP, etc. FIG 3 illustrates an example process of processing the feature layer 110, in which the feature layer 110 exposed through the openings OP is etched to form a feature pattern 110P.

[0090] 4, the photoresist pattern 130P remaining on the feature pattern 110P is removed from the resultant structure of FIG. 3. An ashing and stripping process can be used to remove the photoresist pattern 130P.

[0091] In yet another embodiment, a method for forming a pattern includes the steps of applying a metal-containing resist composition onto a substrate, applying the metal-containing resist edge bead removal composition along an edge of the substrate, drying and heating to form a metal-containing resist film on the substrate, exposing the metal-containing photoresist film to light, and developing using the metal-containing resist developer composition.

[0092] The specific method for each step is as described above. By simultaneously using the composition for removing edge bead of a metal-containing resist or the developer composition for a metal-containing resist according to the present invention in the edge bead removal step and the development step, the edge bead removal effect and the solubility of the unexposed area can be effectively improved, thereby satisfying the requirements for processing and patterning of smaller features and realizing excellent contrast characteristics, excellent sensitivity, and reduced line edge roughness (LER). EXAMPLES

[0093] The present invention will be described in more detail with reference to the following examples of the preparation of the above-mentioned composition for removing edge bead of metal-containing resist and the developer composition for metal-containing resist. However, the technical features of the present invention are not limited to the following examples.

[0094] Preparation of edge bead removal / developer compositions for metal-containing resists Example 1 Difluoroacetic acid and propylene glycol methyl ether acetate (PGMEA) as a solvent are mixed according to the composition shown in Table 1, and then the mixture is shaken at room temperature (25°C) to completely dissolve it. The mixture is then passed through a PTFE filter with a pore size of 1 μm to obtain the final composition.

[0095] Examples 2 to 6, Comparative Examples 1 and 2 A composition was obtained in the same manner as in Example 1, except that the composition was changed to that shown in Table 1 below.

[0096] [Table 1]

[0097] *DFAA: Difluoroacetic acid *DFPA: 2,2-difluoropropionic acid *AA: Acetic acid

[0098] Preparation of organometallic photoresist compositions An organometallic compound having the following chemical formula C was dissolved in 4-methyl-2-pentanol to a concentration of 1 wt %, and then filtered through a 0.1 μm PTFE syringe filter to prepare a photoresist composition. [ka]

[0099] Evaluation: Evaluation of contrast performance and sensitivity The metal-containing photoresist (PR) composition prepared above was spin-coated on an 8-inch wafer at 1,500 rpm for 30 seconds, and then heat-treated at 160° C. for 60 seconds to prepare a coated wafer.

[0100] This was exposed to a 1.2cm x 0.9cm rectangular pattern using a KrF scanner (ASML's PAS5500 / 700D) at a dose of 10 to 100 mJ, then heat-treated at 160°C for 90 seconds, and developed using developer compositions according to Examples 1 to 6 and Comparative Examples 1 to 2, respectively, and finally heat-treated at 240°C for 60 seconds to complete a patterned wafer. The thickness of each exposed portion of the patterned wafer was measured to obtain a contrast curve, which is shown in FIG. 5. From this, the contrast performance (γ(contrast)) and sensitivity (D 100 ) was calculated, and the results are shown in Table 2 below.

[0101] γ(contrast)=1 / log(D 100 / D0) D 100 = Exposure at which PR begins to remain at 100% D0 = exposure dose at which PR is completely removed

[0102] [Table 2]

[0103] FIG. 5 shows contrast curves obtained by measuring the thickness of each exposed portion of a patterned wafer.

[0104] Referring to FIG. 5, it can be seen from the slope of the resolution curve that the second embodiment provides a better resolution.

[0105] In addition, referring to Table 2, it can be seen that the application of the metal-containing photoresist developer composition according to the embodiment shows superior contrast performance and superior sensitivity characteristics compared to the application of the metal-containing photoresist developer composition according to the comparative example.

[0106] Although specific embodiments of the present invention have been described and illustrated above, it is obvious to those skilled in the art that the present invention is not limited to the described embodiments, and that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modifications or variations should not be understood individually from the technical spirit and perspective of the present invention, and the modified embodiments should be considered to belong to the scope of the claims of the present invention. [Explanation of symbols]

[0107] 1...substrate support, 2...spray nozzle, 10...photoresist solution, 12...edge bead, 100...substrate, OP...opening.

Claims

1. A C1-C10 carboxylic acid compound substituted with at least one fluorine atom; and Organic solvents 1. A composition for edge bead removal of a metal-containing resist or a developer composition for a metal-containing resist comprising:

2. The composition for removing edge bead of a metal-containing resist or the developer composition for a metal-containing resist according to claim 1, wherein the at least one fluorine-substituted C1 to C10 carboxylic acid compound is represented by the following Chemical Formula 1: 【Chemistry 1】 (In the above Chemical Formula 1, R １ ~R ３ are each independently hydrogen, fluorine, a fluorine-containing group, or a substituted or unsubstituted C1-C5 alkyl group; n is an integer from 1 to 5; R １ ~R ３ At least one of is fluorine or a fluorine-containing group.

3. The R ２ and the R ３ 3. The metal-containing resist edge bead removal composition or metal-containing resist developer composition of claim 2, wherein at least one of: is fluorine or a fluorine-containing group.

4. The R ２ and the R ３ The metal-containing resist edge bead removal composition or metal-containing resist developer composition of claim 2 , wherein each of is independently fluorine or a fluorine-containing group.

5. The R ２ and the R ３ The composition for removing edge bead of a metal-containing resist or the developer composition for a metal-containing resist according to claim 2 , wherein each of is independently fluorine.

6. The composition for removing edge bead of a metal-containing resist or the developer composition for a metal-containing resist according to claim 1, wherein the at least one fluorine-substituted C1-C10 carboxylic acid compound is at least one of difluoroacetic acid, 2,2-difluoropropionic acid, trifluoroacetic acid, and monofluoroacetic acid.

7. 0.01 to 5% by weight of the at least one fluorine-substituted C1 to C10 carboxylic acid compound based on the total weight of the composition; and 2. The composition for removing edge bead of a metal-containing resist or the developer composition for a metal-containing resist according to claim 1, wherein the organic solvent is contained in an amount of 95 to 99.99% by weight based on the total amount of the composition.

8. 2. The composition for removing edge bead of a metal-containing resist or the developer composition for a metal-containing resist according to claim 1, wherein the metal compound contained in the metal-containing resist includes at least one of an organic oxy group-containing tin compound and an organic carbonyloxy group-containing tin compound.

9. The composition for removing edge bead of a metal-containing resist or the developer composition for 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 2: 【Chemistry 2】 (In the above Chemical Formula 2, R ４ 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 C7 to C30 arylalkyl group, and L ａ -O-R ａ (Here, L ａ is a substituted or unsubstituted C1 to C20 alkylene group, R ａ is a substituted or unsubstituted C1-C20 alkyl group or a substituted or unsubstituted C6-C20 aryl group; R ５ ~R ７ are each independently a halogen, 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 C7 to C30 arylalkyl group, alkoxo and aryloxo (-OR ｂ , where R ｂ 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; a carboxyl group (-O(CO)R ６ , R ６ is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an alkylamide or a dialkylamide (-NR ７ R ８ , where R ７ and R ８ are each independently 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), an amidate (—NR ９ (C.O.R. １０ ), where R ９ and R １０ are each independently 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), or an amidinate (—NR １１ C (NR １２ ) R １３ , where R １１ , R １２ and R １３ are each independently 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; At least one of R5 to R7 is an alkoxo or aryloxo (—OR ｂ , where R ｂ 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; a carboxyl group (-O(CO)R ６ , R ６ is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an alkylamide or a dialkylamide (-NR ７ R ８ , where R ７ and R ８ are each independently 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), an amidate (—NR ９ (C.O.R. １０ ), where R ９ and R １０ are each independently 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), or an amidinate (—NR １１ C (NR １２ ) R １３ , where R １１ , R １２ and R １３ are each independently a hydrogen atom, 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; exposing the metal-containing photoresist film to light; and A patterning method comprising a development step.

11. applying a metal-containing resist composition onto a substrate; Edge bead removal of metal-containing resist; a heat treatment step of drying and heating to form a metal-containing resist film on the substrate; exposing the metal-containing photoresist film to light; and A method for forming a pattern, comprising the step of developing a metal-containing resist using the developer composition according to any one of claims 1 to 9.

12. 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; exposing the metal-containing photoresist film to light; and A method for forming a pattern, comprising the step of developing a metal-containing resist using the developer composition according to any one of claims 1 to 9.

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