A composition for removing edge beads from metal-containing resists or a developer composition for metal-containing resists, and a pattern formation 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 beads from metal-containing resists or a developer composition for metal-containing resists, and a pattern formation method using the same. [Background technology]

[0002] Recently, the semiconductor industry has seen a continuous reduction in critical dimensions, and this reduction in dimensions has led to a demand for new types of high-performance photoresist materials and patterning methods to meet the requirements for processing and patterning increasingly smaller features.

[0003] Furthermore, the recent dramatic development of the semiconductor industry has created a demand for faster operating speeds and larger storage capacities in semiconductor devices. In line with these demands, process technologies that improve the integration density, reliability, and response speed of semiconductor devices are being developed. In particular, it is important to precisely control / implant impurities into the working regions of the silicon substrate so that these regions are interconnected to form elements and ultra-high-density integrated circuits, which can be achieved through the photolithography process. In other words, it has become important to consider the integration of the photolithography process, which involves coating a substrate with photoresist, selectively exposing it with 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 mainly applied onto the substrate while rotating the silicon substrate. However, 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 subsequent semiconductor processes such as etching and ion implantation processes. 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 EBR (EDGE BEAD REMOVAL) process, is carried out. In the EBR process, a composition that exhibits excellent solubility in the photoresist and effectively removes the beads and photoresist remaining on the substrate without generating resist residues is required.

[0005] In addition, there is a need to develop a photoresist that can ensure excellent etching resistance and resolution in the photolithography process, and at the same time improve sensitivity and CD (critical dimension) uniformity, and can improve the LER (line edge roughness) characteristics, as well as a developer composition that can achieve this.

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0006] One embodiment provides a composition for removing edge beads of a metal-containing resist or a developer composition for a metal-containing resist.

[0007] Another embodiment provides a pattern formation method using the composition.

MEANS FOR SOLVING THE PROBLEMS

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

[0009] The pattern formation method according to another embodiment includes the steps of applying a metal-containing resist composition on a substrate, applying a composition for removing edge beads of the aforementioned metal-containing resist along the edge of the substrate, a heat treatment step of drying and heating to form a metal-containing resist film on the substrate, an exposure step of exposing the metal-containing photoresist film; and a development step.

[0010] The pattern formation method according to still another embodiment includes the steps of applying a metal-containing resist composition on a substrate, an edge bead removal step of the metal-containing resist, a heat treatment step of drying and heating to form a metal-containing resist film on the substrate, an exposure step of exposing the metal-containing photoresist film; and a development step of developing using the aforementioned developer composition of the metal-containing resist.

[0011] The pattern formation method according to still another embodiment includes the steps of applying a composition for removing edge beads of the aforementioned metal-containing resist along the edge of the substrate, a heat treatment step of drying and heating to form a metal-containing resist film on the substrate, an exposure step of exposing the metal-containing photoresist film; and a development step of developing using the aforementioned developer composition of the metal-containing resist.

Advantages of the Invention

[0012] The composition for removing edge beads of a metal-containing resist according to one embodiment can reduce metal-based contamination inherent in the metal-containing resist and remove the resist applied to the edge and back surface of the substrate, thereby meeting the requirements for processing and patterning smaller features.

[0013] The metal-containing developer composition according to another embodiment can minimize defects present in the metal-containing photoresist film after the exposure process and enable easy development, thereby realizing excellent contrast characteristics, excellent sensitivity, and reduced line edge roughness (LER).

Brief Description of the Drawings

[0014] [Figure 1] This is a schematic diagram showing a photoresist coating apparatus. [Figure 2] This is a cross-sectional view showing the process sequence to illustrate the pattern formation method. [Figure 3] This is a cross-sectional view showing the process sequence to illustrate the pattern formation method. [Figure 4] This is a cross-sectional view showing the process sequence to illustrate the pattern formation method. [Figure 5] This is a contrast curve obtained by measuring the thickness of each exposed area on a patterned wafer. [Modes for carrying out the invention]

[0015] The embodiments of the present invention will be described in detail below with reference to the attached drawings. However, in order to clarify the gist of this description, explanations of functions or configurations that are already known will be omitted.

[0016] To clearly explain this description, unnecessary explanatory parts have been omitted, and the same or similar components are denoted by the same reference numerals throughout the specification. Furthermore, the dimensions and thicknesses of each component shown in the drawings are arbitrarily shown for the sake of explanation, and this description is not necessarily limited to those shown in the drawings.

[0017] In the drawings, the thicknesses were enlarged to clearly represent multiple layers and regions. Furthermore, in the drawings, the thicknesses of some layers and regions were exaggerated for explanatory purposes. When a layer, film, region, plate, or other part is described as being "on top" of another part, this includes not only cases where it is "directly above" another part, but also cases where another part lies in between.

[0018] In this description, "substituted" means that the hydrogen atom is substituted with deuterium, a halogen group, a hydroxyl 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 substituted by another substituent.

[0019] In this document, "alkyl group" refers to a linear or branched aliphatic hydrocarbon group unless otherwise defined. An 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 one in which the alkyl chain contains 1 to 5 carbon atoms, and is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0021] The alkyl groups mentioned above refer to specific examples such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and hexyl groups.

[0022] In the chemical formulas described herein, t-Bu represents the tert-butyl group.

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

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

[0025] In this document, unless otherwise defined, "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 document, unless otherwise defined, "alkenyl group" refers to a linear or branched aliphatic hydrocarbon group containing one or more double bonds, specifically an aliphatic unsaturated alkenyl group.

[0027] In this document, "alkynyl group" refers to a linear or branched aliphatic hydrocarbon group containing one or more triple bonds, and means an aliphatic unsaturated alkynyl group unless otherwise defined.

[0028] In this description, "aryl group" refers to a substituent in which all elements of the cyclic substituent have p-orbitals, and these p-orbitals form a conjugation, and includes monocyclic or fusion-ring polycyclic (i.e., rings that share adjacent pairs of carbon atoms) active groups.

[0029] In this description, a "heteroaryl group" means 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 sigma bonds, or, if the heteroaryl group contains two or more rings, the two or more rings may be fused together. If 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-C30 aryl groups may be, but are not limited to, substituted or unsubstituted phenyl groups, substituted or unsubstituted naphthyl groups, substituted or unsubstituted anthracenyl groups, substituted or unsubstituted phenantrenyl groups, substituted or unsubstituted naphthacenyl groups, substituted or unsubstituted pyrenyl groups, substituted or unsubstituted biphenyl groups, substituted or unsubstituted p-terphenyl groups, substituted or unsubstituted m-terphenyl groups, substituted or unsubstituted o-terphenyl groups, substituted or unsubstituted chrysenyl groups, substituted or unsubstituted benzophenantrenyl groups, substituted or unsubstituted triphenylene groups, substituted or unsubstituted perilennyl groups, substituted or unsubstituted fluorenyl groups, substituted or unsubstituted indenyl groups, or combinations thereof.

[0031] More specifically, substituted or unsubstituted C2-C30 heterocyclic groups include substituted or unsubstituted furanyl groups, substituted or unsubstituted thiophenyl groups, substituted or unsubstituted pyrrolyl groups, substituted or unsubstituted pyrazolyl groups, substituted or unsubstituted imidazolyl groups, substituted or unsubstituted triazolyl groups, substituted or unsubstituted oxazolyl groups, substituted or unsubstituted thiazolyl groups, substituted or unsubstituted oxadiazolyl groups, substituted or unsubstituted thiadiazolyl groups, substituted or unsubstituted pyridyl groups, substituted or unsubstituted pyrimidinyl groups, substituted or unsubstituted pyrazinyl groups, substituted or unsubstituted triazinyl groups, substituted or unsubstituted benzofuranyl groups, substituted or unsubstituted benzothiophenyl groups, substituted or unsubstituted benzimidazolyl groups, substituted or unsubstituted indolyl groups, substituted or unsubstituted quinolinyl groups, and substituted or unsubstituted The group may be, but is not limited to, an unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthilidinyl group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzothiadinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted benzonaphthofuranyl group, a substituted or unsubstituted benzonaphthothiophenyl group, a substituted or unsubstituted benzofuranofurenyl group, a substituted or unsubstituted benzothiophenfluorenyl group, or a combination thereof.

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

[0033] Referring to Figure 1, a substrate support section 1 on which the substrate W is placed is provided, and the substrate support section 1 includes a spin chuck or a spin coater, etc.

[0034] The substrate support unit 1 rotates in a first direction at a predetermined rotational speed, providing centrifugal force to the substrate W. An injection nozzle 2 is located on the substrate support unit 1, and the injection nozzle 2 is located in an atmospheric area away from the top of the substrate W. During the solution supply stage, it moves to the top of the substrate to spray the photoresist solution 10. As a result, the photoresist solution 10 is applied to the substrate surface by the centrifugal force. At this time, the photoresist solution 10 supplied to the center of the substrate W is applied while spreading to the periphery of the substrate W by the centrifugal force, and a portion of it moves to the side surface of the substrate and the lower surface of the periphery of the substrate.

[0035] In other words, in the coating process, the photoresist solution 10 is mainly applied by a spin coating method, but a predetermined amount of viscous photoresist solution 10 is supplied to the center of the substrate W and gradually diffuses toward the periphery of the substrate by centrifugal force.

[0036] Therefore, the thickness of the photoresist is formed flat by 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 at the periphery of the substrate due to the action of surface tension, and more seriously, the photoresist accumulates up to the bottom surface of the periphery of the substrate, which is called an edge bead 12.

[0038] The following describes a composition for removing edge beads from metal-containing resists or a developer composition for metal-containing resists according to one embodiment.

[0039] A composition for removing edge beads from metal-containing resists or a developer solution composition for metal-containing resists according to one embodiment of the present invention comprises a C1-C10 carboxylic acid compound substituted with at least one fluorine atom, and an organic solvent.

[0040] The C1-C10 carboxylic acid compound, in which at least one fluorine is substituted, can promote the reaction with the photoresist in the exposed area, thereby increasing the solubility difference between the exposed and unexposed areas.

[0041] Moreover, by containing fluorine which is an electron-withdrawing group, it is advantageous for realizing a fine pattern and controlling scum by maintaining an appropriate pKa for improving sensitivity and resolution. [[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​In one embodiment, the composition for removing edge beads from the metal-containing resist or the developer solution composition for the metal-containing resist may contain 0.01 to 5% by weight of at least one fluorine-substituted C1-C10 carboxylic acid compound based on the total amount of the composition, and 95 to 99.99% by weight of an organic solvent based on the total amount of the composition.

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

[0049] As an example of an organic solvent contained in a composition for removing edge beads from metal-containing resists or a developer solution composition according to one embodiment, 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), γ-butyrolactone (GBL), 1-butanol (n-Butanol), ethyl lactate (EL), dienebutyl ether (DBE), diisopropyl ether (DIAE), acetylacetone, butyl lactate (n-Butylactate), 4-methyl-2-pentanol (or methyl isobutyl Examples include, but are not limited to, carbinol (may be described as 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 ethyl acetate, butyl acetate, methyl 2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate, or mixtures thereof.

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

[0051] Furthermore, the metal-containing resist developer composition according to the present invention minimizes defects present in the metal-containing photoresist film after the exposure process, enabling easy development and thereby achieving excellent pattern characteristics.

[0052] Furthermore, it can also achieve superior sensitivity and reduced line edge roughness (LER).

[0053] If other additives described later are included, the organic solvent may be included in the amount remaining after deducting the components that are included.

[0054] The product may further contain at least one other additive selected from surfactants, dispersants, hygroscopic agents, and coupling agents.

[0055] The surfactant can improve the coating uniformity and wettability of the photoresist composition. In exemplary examples, the surfactant may, but is not limited to, sulfate esters, sulfonates, phosphate esters, soaps, amine salts, quaternary ammonium salts, polyethylene glycol, alkylphenol ethylene oxide adducts, polyhydric alcohols, nitrogen-containing vinyl polymers, or combinations thereof. For example, the surfactant may include alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, or quaternary ammonium salts. If the photoresist composition contains the surfactant, the surfactant may be present in an amount of about 0.001% to about 3% by weight based on the total weight of the photoresist composition.

[0056] The dispersant can serve to ensure that each component constituting the photoresist composition is uniformly dispersed within the photoresist composition. In exemplary examples, the dispersant may, but is not limited to, epoxy resin, polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, glycose, sodium dodecyl sulfate, sodium citrate, oleic acid, linoleic acid, or a combination thereof. If the photoresist composition contains the dispersant, the dispersant may be present in an amount of about 0.001% to about 5% by weight based on the total weight of the photoresist composition.

[0057] The hygroscopic agent can play a role in preventing adverse effects of moisture on the photoresist composition. For example, the hygroscopic agent can play a role in preventing the oxidation of metals contained in the photoresist composition by moisture. In exemplary embodiments, the hygroscopic agent may, but is not limited to, polyoxyethylene nonylphenol ether, polyethylene glycol, polypropylene glycol, polyacrylamide, or a combination thereof. When the photoresist composition contains the hygroscopic agent, the hygroscopic agent may be present in an amount of about 0.001% to about 10% by weight based on the total weight of the photoresist composition.

[0058] The coupling agent can play a role in improving the adhesion between the photoresist composition and the underlying film when the photoresist composition is coated onto the underlying film. In exemplary examples, the coupling agent may include a silane coupling agent. The silane coupling agent may consist of, 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 contains the coupling agent, the coupling agent may be present in an amount of about 0.001% to about 5% by weight based on the total weight of the photoresist composition.

[0059] The metal compound contained in the metal-containing resist may include at least one of an organic oxy group-containing tin compound and an organic carbonyl oxy group-containing tin compound.

[0060] As an example, the metal compound contained in the metal-containing resist can be represented by the following chemical formula 2. [ka] In the aforementioned chemical formula 2, R 4 These include substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C7-C30 arylalkyl groups, and L a -OR a (L here) a R is a substituted or unsubstituted C1-C20 alkylene group, a (These are selected from substituted or unsubstituted C1-C20 alkyl groups or substituted or unsubstituted C6-C20 aryl groups.) R 5 ~R 7 These are, independently, halogens, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C7-C30 arylalkyl groups, alkoxos and aryloxos (-OR b , here, R b (which are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), carboxyl groups (-O(CO)R 6 , R 6(which 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), alkylamide or dialkylamide (-NR 7 R 8 , here, R 7 and R 8 Each of these is independently 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), amidato (-NR 9 (COR 10 ), here, R 9 and R 10 Each of these is independently 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), or amidinate (-NR) 11 C(NR 12 )R 13 , here, R 11 , R 12 and R 13 Each of these is independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof. At least one of R5-R7 is an alkoxo and aryloxo (-OR b , here, R b(which are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), carboxyl groups (-O(CO)R 6 , R 6 (which 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), alkylamide or dialkylamide (-NR 7 R 8 , here, R 7 and R 8 Each of these is independently 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), amidato (-NR 9 (COR 10 ), here, R 9 and R 10 Each of these is independently 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), or amidinate (-NR) 11 C(NR 12 )R 13 , here, R 11 , R 12 and R 13Each of these is independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof.

[0061] For example, the metal compound contained in the metal-containing resist may be at least one of alkyloxy group-containing tin compounds and alkylcarbonyloxy group-containing tin compounds.

[0062] On the other hand, according to another embodiment, a pattern forming method may be provided that includes the step of removing edge beads using the aforementioned metal-containing resist edge bead removal composition. As an example, the manufactured pattern may be a photoresist pattern. More specifically, it may be a negative-type photoresist pattern.

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

[0064] More specifically, the step of forming a pattern using a metal-containing resist composition may include the steps 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 drying the applied metal-containing resist composition to form a photoresist film. The metal-containing resist composition may contain a tin-based compound, for example, the tin-based compound may contain at least one of an organic oxy group-containing tin compound and an organic carbonyl oxy group-containing tin compound.

[0065] More specifically, the process may include a step of applying an appropriate amount of the aforementioned metal-containing resist edge bead removal composition along the edge of the substrate while rotating (spinning) the substrate at an appropriate speed (e.g., 500 rpm or more).

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

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

[0068] As an example, examples of light that can be used in the exposure process include not only short-wavelength light such as i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm), and ArF excimer laser (wavelength 193nm) as activation irradiation lines, but also high-energy wavelength light such as EUV (Extreme UltraViolet; wavelength 13.5nm) and E-Beam (electron beam).

[0069] More specifically, the exposure light according to one 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] During the process of forming the photoresist pattern, a negative-type pattern can be formed.

[0071] In a photoresist film, the exposed regions form polymers through crosslinking reactions such as condensation between organometallic compounds, resulting in different solubility levels from the unexposed regions of the photoresist film.

[0072] Next, a second heat treatment step is performed on the substrate. This second heat treatment step can be carried out at a temperature of approximately 90°C to approximately 200°C. By performing this second heat treatment step, the exposed area of ​​the photoresist film becomes difficult to dissolve in the developer solution.

[0073] Specifically, the photoresist pattern corresponding to the negative tone image can be completed by dissolving the photoresist film corresponding to the unexposed region using an organic solvent such as 2-heptanone, and then removing it.

[0074] The developer used in the pattern formation method according to one embodiment may be an organic solvent, and examples include ketones such as methyl ethyl ketone, acetone, cyclohexanone, and 2-heptanone; alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, and methanol; esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, and butyrolactone; aromatic compounds such as benzene, xylene, and toluene; or combinations thereof.

[0075] As mentioned above, photoresist patterns formed by exposure with light having wavelengths such as i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm), and ArF excimer laser (wavelength 193nm), as well as high-energy light such as EUV (Extreme UltraViolet; wavelength 13.5nm) and E-Beam (electron beam), can have a width of 5nm to 100nm in thickness. For example, the photoresist patterns can be formed with widths of 5nm to 90nm, 5nm to 80nm, 5nm to 70nm, 5nm to 60nm, 5nm to 50nm, 5nm to 40nm, 5nm to 30nm, and 5nm to 20nm in thickness.

[0076] On the other hand, the photoresist pattern may have a half-pitch of approximately 50 nm or less, for example 40 nm or less, for example 30 nm or less, for example 20 nm or less, for example 15 nm or less, and a pitch having a line width roughness of approximately 10 nm or less, approximately 5 nm or less, approximately 3 nm or less, or approximately 2 nm or less.

[0077] Another embodiment of the pattern formation method includes the steps of applying a metal-containing resist composition onto a substrate, removing edge beads of the metal-containing resist, a heat treatment step of drying and heating to form a metal-containing resist film on the substrate, an exposure step of the metal-containing photoresist film, and developing using the aforementioned metal-containing resist developer composition.

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

[0079] The edge bead removal step for metal-containing resists can be performed by applying an appropriate amount of a commonly known organic solvent or composition for edge bead removal along the edge of the substrate while rotating (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] By using the aforementioned metal-containing resist developer composition to dissolve and then remove the photoresist film corresponding to the unexposed areas, a photoresist pattern corresponding to the negative tone image can be completed.

[0083] The following explains in detail, using a diagram as an example, how to develop and form a pattern.

[0084] Figures 2 to 4 are cross-sectional views illustrating the pattern formation method in order of the process steps.

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

[0086] In an exemplary embodiment, the exposed photoresist film can be developed to remove the unexposed regions of the photoresist film, thereby forming a photoresist pattern 130P consisting of the exposed regions of the photoresist film. The photoresist pattern 130P may include a plurality of apertures OP.

[0087] In the exemplary embodiment, the photoresist film can be developed using a negative-tone development (NTD) process. In this case, a metal-containing photoresist developer composition according to one embodiment can be used as the developer composition.

[0088] Referring to Figure 3, the feature layer 110 is fabricated using the photoresist pattern 130P from the result in Figure 2.

[0089] For example, various processes can be performed to process the feature layer 110, such as etching the feature layer 110 exposed through the opening OP of the photoresist pattern 130P, implanting impurity ions into the feature layer 110, forming an additional film on the feature layer 110 through the opening OP, and deforming a part of the feature layer 110 through the opening OP. Figure 3 illustrates an example of a process for processing the feature layer 110, which involves etching the feature layer 110 exposed through the opening OP to form the feature pattern 110P.

[0090] Referring to Figure 4, the photoresist pattern 130P remaining on the feature pattern 110P is removed from the result in Figure 3. Ashing and stripping processes can be used to remove the photoresist pattern 130P.

[0091] Another embodiment of the pattern formation method includes the steps of: applying a metal-containing resist composition onto a substrate; applying the aforementioned metal-containing resist edge bead removal composition along the edge of the substrate; a heat treatment step of drying and heating to form a metal-containing resist film on the substrate; exposing the metal-containing photoresist film; and developing it using the aforementioned metal-containing resist developer composition.

[0092] The specific methods for each stage are as described above. By simultaneously utilizing the edge bead removal composition for metal-containing resists or the developer solution composition for metal-containing resists according to the present invention in the edge bead removal stage and the development stage, the edge bead removal effect and the solubility of unexposed areas are effectively improved, thereby meeting the requirements for processing and patterning smaller features and achieving excellent contrast characteristics, superior sensitivity, and reduced line edge roughness (LER). [Examples]

[0093] The present invention will be described in more detail below through examples relating to the production of the aforementioned metal-containing resist edge bead removal composition and metal-containing resist developer composition. However, the technical features of the present invention are not limited by the following examples.

[0094] Manufacturing of compositions for removing edge beads from metal-containing resists / developer compositions 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 shaken at room temperature (25°C) to completely dissolve. 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 Example 1 and Comparative Example 2 The composition is obtained in the same manner as in Example 1, except that the composition is changed to that shown in Table 1 below.

[0096] [Table 1]

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

[0098] Manufacturing of organometallic photoresist compositions An organometallic compound having the structure of chemical formula C shown below 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 produce a photoresist composition. [ka]

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

[0100] Using a KrF scanner (ASML PAS5500 / 700D), a rectangular pattern measuring 1.2 cm x 0.9 cm was exposed with a dose of 10-100 mJ. The wafers were then heat-treated at 160°C for 90 seconds, developed using the developer compositions from Examples 1-6 and Comparative Examples 1-2, respectively, and finally heat-treated at 240°C for 60 seconds to complete the patterned wafers. The contrast curves obtained by measuring the thickness of each exposed area on the patterned wafers are shown in Figure 5. From these, the contrast performance (γ (contrast)) and sensitivity (D) were determined. 100 The result was calculated and is shown in Table 2 below.

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

[0102] [Table 2]

[0103] Figure 5 shows the contrast curve obtained by measuring the thickness of each exposed area on a patterned wafer.

[0104] Referring to Figure 5, it can be seen from the slope of the resolution curve that a better resolution is achieved in Example 2.

[0105] Furthermore, referring to Table 2, it can be confirmed that when the metal-containing photoresist developer composition according to the examples is applied, it exhibits superior contrast performance and superior sensitivity characteristics compared to when the metal-containing photoresist developer composition according to the comparative examples is applied.

[0106] Although specific embodiments of the present invention have been described and illustrated above, it will be obvious to those ordinary skill in the art that the present invention is not limited to the described embodiments and can be modified and transformed in various ways without departing from the spirit and scope of the invention. Therefore, such modifications or variations should not be understood individually from the technical spirit or viewpoint of the invention, and the modified embodiments can be said to fall within the scope of the claims of the present invention. [Explanation of Symbols]

[0107] 1...Substrate support part, 2...Injection nozzle, 10...Photoresist solution, 12...Edge bead, 100...Substrate, OP...Opening.

Claims

1. C1-C10 carboxylic acid compounds in which at least one fluorine is substituted, represented by the following chemical formula 1; and Organic solvents A composition for removing edge beads from metal-containing resists or a developer composition for metal-containing resists, comprising: The metal compound contained in the metal-containing resist is a composition for removing edge beads from a metal-containing resist or a developer composition for a metal-containing resist, represented by the following general formula (2). 【Chemistry 1】 (In the above chemical formula 1, R １ is hydrogen or a substituted or unsubstituted C1-C5 alkyl group, R ２ ~R ３ Each of these is independently either fluorine or a fluorine-containing group. n is one of the integers from 1 to 5. 【Chemistry 2】 (In the above chemical formula 2, R ４ These include substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C7-C30 arylalkyl groups, and L ａ -O-R ａ (Here L ａ R is a substituted or unsubstituted C1-C20 alkylene group, ａ (is selected from substituted or unsubstituted C1-C20 alkyl groups or substituted or unsubstituted C6-C20 aryl groups) R ５ to R ７ are each independently halogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, alkoxo and aryloxo (-OR ｂ , where R ｂ is 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), 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), alkylamide or dialkylamide (-NR ７ R ８ , where R ７ and R ８ are each independently 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), amidato (-NR ９ (COR １０ ), where R ９ and R １０ Each of these is independently 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), or amidinate (amidinato) (-NR １１ C (NR １２ ) R １３ Here, R １１ , R １２ and R １３ Each of these is independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof. R ５ ~R ７ At least one of them is an alcoxo and an aryl oxo (-OR ｂ Here, R ｂ (These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), carboxyl groups (-O(CO)R ６ , R ６ (-NR) ７ R ８ Here, R ７ and R ８ Each of these is independently 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), amidate (amidato) (-NR ９ (COR １０ ), here, R ９ and R １０ Each of these is independently 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), or amidinate (amidinato) (-NR １１ C (NR １２ ) R １３ Here, R １１ , R １２ and R １３ Each of these is independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof.

2. The aforementioned R ２ and R ３ The composition for removing edge beads from a metal-containing resist or the developer composition for a metal-containing resist according to claim 1, wherein each of these is independently fluorine.

3. The metal-containing resist edge bead removal composition or metal-containing resist developer composition according to claim 1, wherein the C1-C10 carboxylic acid compound represented by chemical formula 1, which is substituted with at least one fluorine, is at least one of difluoroacetic acid, 2,2-difluoropropionic acid, and monofluoroacetic acid.

4. The composition contains 0.01 to 5% by weight of at least one fluorine-substituted C1 to C10 carboxylic acid compound represented by the chemical formula 1, and The composition for removing edge beads from metal-containing resists or the developer composition for metal-containing resists according to claim 1, comprising 95 to 99.99% by weight of the organic solvent relative to the total amount of the composition.

5. The step of applying a metal-containing resist composition onto a substrate; A step of applying the metal-containing resist edge bead removal composition according to any one of claims 1 to 4 along the edge of the substrate; A heat treatment step in which a metal-containing resist film is formed on the substrate by drying and heating; The step of exposing the metal-containing photoresist film; and A pattern formation method, including a development step.

6. The step of applying a metal-containing resist composition onto a substrate; Edge bead removal stage for metal-containing resist; A heat treatment step in which a metal-containing resist film is formed on the substrate by drying and heating; The step of exposing the metal-containing photoresist film; and A method for forming a pattern, comprising the step of developing using a metal-containing resist developer composition according to any one of claims 1 to 4.

7. The step of applying a metal-containing resist composition onto a substrate; A step of applying the metal-containing resist edge bead removal composition according to any one of claims 1 to 4 along the edge of the substrate; A heat treatment step in which a metal-containing resist film is formed on the substrate by drying and heating; A method for forming a pattern, comprising the steps of: exposing the metal-containing photoresist film; and developing the metal-containing resist using the developing solution composition described in any one of claims 1 to 4.

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