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

Abstract

To provide a composition for removing an edge bead of a metal-containing resist, and a pattern forming method using the same.SOLUTION: The composition for removing the edge bead of the metal-containing resist contains at least one alcoholic compound selected from among organic solvents, diol compounds and cyclic alcohol compounds and an acid compound having a pKa1 of 1.0 ≤ pKa1 ≤ 4.5, and 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 and a patterning method using the same. [Background technology]

[0002] With the recent semiconductor industry continuing to shrink critical dimensions, new types of high performance photoresist materials and patterning methods are required to meet the needs of processing and patterning smaller and smaller features.

[0003] Furthermore, with the recent rapid development of the semiconductor industry, semiconductor devices are required to have higher operating speeds and larger memory capacities. To meet these needs, process technologies are being developed to improve the integration, reliability, and response speed of semiconductor devices. It is particularly important to precisely control and inject impurities into active regions of silicon substrates so that these regions are interconnected to form elements and ultra-high-density direct circuits, which can be achieved through photolithography processes. Specifically, it is becoming increasingly important to consider photolithography process integration, which involves coating a photoresist on a substrate, selectively exposing it to ultraviolet (including extreme ultraviolet), electron beams, or X-rays, and then developing it.

[0004] In particular, in the process of forming a photoresist layer, resist is typically applied to the substrate while the substrate is rotated. During this process, resist is also applied to the edge and backside of the substrate, which can cause indentation or pattern defects in subsequent semiconductor processes such as etching and ion implantation. Therefore, a process of stripping and removing the photoresist applied to the edge and backside of the silicon substrate using a thinner composition, i.e., 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. Summary of the Invention [Problem to be solved by the invention]

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

[0006] Another embodiment provides a pattern forming method using the composition.

[0007] A composition for removing edge bead of a metal-containing resist according to one embodiment includes an organic solvent, at least one alcohol compound selected from diol compounds and cyclic alcohol compounds, and an acid compound having a pKa1 of 1.0≦pKa1≦4.5.

[0008] A pattern formation method according to another embodiment includes the steps of: applying a metal-containing resist composition onto a substrate; applying a composition for removing edge bead of a metal-containing resist along an edge of the substrate; performing a heat treatment by drying and heating to form a metal-containing resist film on the substrate; and exposing and developing to form a resist pattern.

[0009] The composition for removing edge bead of metal-containing resist according to one embodiment can meet the demand for processing and patterning smaller features by reducing metal substrate contamination inherent in metal-containing resist and removing resist applied to the edge and backside of the substrate. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic diagram showing a photoresist coating apparatus. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, in the following description, descriptions of already known functions or configurations will be omitted in order to clarify the gist of the description.

[0012] In order to clarify the present description, parts that are not relevant to the description will be omitted, and the same or similar components will be 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 description, and the present description is not necessarily limited to those shown in the drawings.

[0013] In the drawings, thicknesses of multiple layers and regions are exaggerated to clearly show them. Also, in the drawings, thicknesses of some layers and regions are exaggerated for ease of explanation. When a layer, film, region, plate, or other portion is "on" or "above" another portion, this includes not only when it is "directly on" the other portion, but also when there is another portion between them.

[0014] In this description, "substituted" means that a hydrogen atom is replaced with deuterium, a halogen group, a hydroxy group, a thiol group, a cyano group, a carbonyl group, a carboxyl group, an amino group, an amide group, an ester group, a substituted or unsubstituted C1-C30 amine group, a nitro group, a substituted or unsubstituted C1-40 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 is not replaced with another substituent and remains a hydrogen atom.

[0015] In this specification, unless otherwise defined, the term "alkyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0016] The alkyl group may be a C1 to C20 alkyl group. More specifically, the alkyl group may be a C1 to C10 alkyl group or a C1 to C6 alkyl group. For example, a C1 to C5 alkyl group means that 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, tert-butyl, n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, and sec-isopentyl.

[0017] 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.

[0018] In the formulae depicted herein, t-Bu refers to a tert-butyl group.

[0019] Unless otherwise defined, the term "cycloalkyl group" used herein refers to a monovalent cyclic aliphatic hydrocarbon group.

[0020] The cycloalkyl group means a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or the like.

[0021] The cycloalkyl group may be a C3 to C10 cycloalkyl group, such as a C3 to C8 cycloalkyl group, a C3 to C7 cycloalkyl group, or a C3 to 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.

[0022] As used herein, unless otherwise defined, the term "heterocycloalkyl group" means that the cycloalkyl group contains at least one heteroatom selected from the group consisting of N, O, S, S, P, and Si.

[0023] In this description, unless otherwise defined, the term "alkenyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group that is an aliphatic unsaturated alkenyl group containing one or more double bonds.

[0024] In this description, unless otherwise defined, the term "alkynyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group, an aliphatic unsaturated alkynyl group containing one or more triple bonds.

[0025] In this description, the term "aryl group" refers to a substituent in which all elements of the cyclic substituent have p-orbitals and these p-orbitals form conjugation, including monocyclyl or fused-ring polycyclyl (i.e., rings that share adjacent pairs of carbon atoms) functionalities.

[0026] As used herein, the term "heteroaryl group" refers to an aryl group containing at least one heteroatom selected from the group consisting of N, O, S, S, P, and Si. Two or more heteroaryl groups may be directly linked via a sigma bond, or, if the heteroaryl group contains two or more rings, the two or more rings may be fused to each other. If the heteroaryl group is a fused ring, each ring may contain 1 to 3 heteroatoms.

[0027] More specifically, the alkyl group may be, but is not limited to, a substituted or unsubstituted C6 to C30 aryl group, 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.

[0028] More specifically, the substituted or unsubstituted C2-C30 heterocycle 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 indoleyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted benzophenone ... The alkyl 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 naphthyridinyl group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzothiazinyl 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 benzonaphthufuranyl group, a substituted or unsubstituted benzonaphthothiophenyl group, a substituted or unsubstituted benzofuranofluorenyl group, a substituted or unsubstituted benzothienofluorenyl group, or a combination thereof.

[0029] FIG. 1 is a schematic diagram showing a photoresist coating apparatus.

[0030] Referring to FIG. 1, a substrate support 1 on which a substrate (W) is placed is provided, and the substrate support 1 includes a spin chuck or a spin coater.

[0031] The substrate support 1 rotates in a first direction at a predetermined rotational speed to apply centrifugal force to the substrate (W). A spray nozzle 2 is located on the substrate support 1. The spray nozzle 2 is located in a standby area away from the top of the substrate (W) and moves to the top of the substrate during the solution supply step to spray the photoresist solution 10. As a result, the photoresist solution 10 is applied to the surface of the substrate by the centrifugal force. At this time, the photoresist solution 10 supplied to the center of the substrate (W) spreads to the edge of the substrate (W) by the centrifugal force, and some of it moves to the side and under-etched surface of the substrate.

[0032] That is, in the coating process, the photoresist solution 10 is mainly applied by spin coating, in which a predetermined amount of viscous photoresist solution 10 is supplied to the center of the substrate (W), and gradually spreads in the etching direction of the substrate by centrifugal force.

[0033] Therefore, the thickness of the photoresist is formed evenly depending on the rotation speed of the substrate support.

[0034] However, as the solvent evaporates, the viscosity gradually increases, and due to the effect of surface tension, a relatively large amount of photoresist accumulates on the etched surface of the substrate. More seriously, the photoresist accumulates on the underside of the etched surface of the substrate, which is called an edge bead 12.

[0035] An embodiment of a composition for removing edge bead of a metal-containing resist will now be described.

[0036] A composition for removing edge beads of a metal-containing resist according to one embodiment of the present invention includes an organic solvent, at least one alcohol-based compound selected from diol compounds and cyclic alcohol compounds, and an acid compound having a pKa1 of 1.0≦pKa1≦4.5.

[0037] The composition for removing edge beads of metal-containing resist contains a cyclic compound substituted with a hydroxy group (-OH), and the hydroxy group (-OH) forms a coordinate bond with the metal-containing resist, so by applying a composition containing this, the metal-containing resist can be effectively removed.

[0038] Specifically, the diol compound is represented by the following Chemical Formula 1 or Chemical Formula 2. [ka]

[0039] In the above Chemical Formula 1 and Chemical Formula 2, R 1 ~R 10 are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a nitro group, a substituted or unsubstituted C1 to C30 amine group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group; R 1 ~R 5 one of which is a hydroxy group, R 6 ~R 10 one of which is a hydroxy group, n is an integer from 1 to 10.

[0040] More specifically, the formula 1 is represented by the following formula 1-1. [ka]

[0041] Moreover, the chemical formula 2 is represented by any one of the following chemical formulas 2-1 to 2-3. [ka]

[0042] In the above Chemical Formula 1-1 and Chemical Formula 2-1 to Chemical Formula 2-3, R 1 ~R4 , R 6 ~R 10 and n is defined as above.

[0043] Specifically, the cyclic alcohol compound is represented by the following chemical formula 3: [ka]

[0044] In the above Chemical Formula 3, R 11 ~R 16 are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a nitro group, a substituted or unsubstituted C1 to C30 amine group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group; R 11 ~R 16 At least one of these is a hydroxy group.

[0045] More specifically, the chemical formula 3 is represented by any one of the following chemical formulas 3-1 to 3-3. [ka]

[0046] In the above Chemical Formulas 3-1 to 3-3, R 11 ~R 16 The definition is as described above.

[0047] For example, the alcohol-based compound may be at least one of pyrocatechol, 4-methylcatechol, 4-chlorocatechol, 4-nitrocatechol, tropolone, and 1,2-ethanediol, or a combination thereof.

[0048] The pKa1 of the acid compound may be 1.0≦pKa1≦4.0.

[0049] The acid compound may be at least one of phosphoric acid, phosphonic acid, methylphosphonic acid, ethylphosphonic acid, butylphosphonic acid, hexylphosphonic acid, n-octylphosphonic acid, tetradecylphosphonic acid, octadecylphosphonic acid, phenylphosphonic acid, vinylphosphonic acid, 6-hydroxyhexylphosphonic acid, decylphosphonic acid, methylenediphosphonic acid, nitrilotrimethylenetriphosphonic acid, diphenylphosphinic acid, bis(4-methoxyphenyl)phosphinic acid, phosphinic acid, bis(hydroxymethyl)phosphinic acid, phenylphosphinic acid, p-(3-aminopropyl)-p-butylphosphinic acid, chloroacetic acid, formic acid, acetic acid, or a combination thereof.

[0050] As an example, the acid compound may be at least one of phosphoric acid, phosphonic acid, methylphosphonic acid, butylphosphonic acid, phenylphosphonic acid, vinylphosphonic acid, chloroacetic acid, formic acid, acetic acid, or a combination thereof.

[0051] The composition for removing edge bead of metal-containing resist can contain 0.05 to 40% by weight of the alcohol-based compound and the acid compound; and 60 to 99.95% by weight of the organic solvent.

[0052] Within the above ranges, the alcohol compound and the acid compound may be contained in an amount of 0.1 to 40% by weight, for example, 0.5 to 40% by weight or 1 to 40% by weight.

[0053] The alcohol compound and the acid compound may be contained in a weight ratio of 1:0.5 to 1:50.

[0054] For example, the alcohol compound and the acid compound may be included in a weight ratio of 1:1 to 1:50, for example, 1:1 to 1:40 or 1:1 to 1:30.

[0055] Within this range, the alcohol compound can comprise less than 10% by weight, specifically less than or equal to 9% by weight, and more specifically less than or equal to 8% by weight.

[0056] Within this range, the acid compound can comprise less than 40 wt%, specifically less than or equal to 35 wt%, and more specifically less than or equal to 30 wt%.

[0057] Examples of organic solvents contained in the composition for removing edge bead of a metal-containing resist 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), lubricating butyrolactone (GBL), 1-butanol (n-Butanol), ethyl lactate (EL), dibutyl ether (DBE), diisopropyl ether (DIAE), acetylacetone, 4-methyl-2-pentanol (or methylisobutyl Examples of suitable hydroxybenzoates include, but are not limited to, methyl 2-hydroxybenzoates (which can be written as methyl carbinol (MIBC)), 1-methoxy-2-propanol, 1-ethoxy-2-propanol, toluene, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl ethylpyruvate, ethyl acetate, butyl acetate, butyl lactate, methyl 2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate, or mixtures thereof.

[0058] 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.

[0059] When other additives described below are included, the organic solvent may be included in the remaining amount excluding the other components.

[0060] The composition may further contain at least one other additive selected from a surfactant, a dispersant, a moisture absorbent, and a coupling agent.

[0061] According to another embodiment, a method for forming a pattern may be provided, which includes removing edge beads using the above-described composition for removing edge beads of a metal-containing resist. For example, the formed pattern may be a photoresist pattern. More specifically, it may be a negative photoresist pattern.

[0062] 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, and exposing and developing to form a resist pattern.

[0063] More specifically, the step of forming a pattern using the metal-containing resist composition may include 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 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.

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

[0065] In the above Chemical Formula 4, R 17is selected from 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, and a substituted or unsubstituted C7 to C30 arylalkyl group; R 18 ~R 20 are each independently 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, alkoxy, and aryloxy (-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 c , R c 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 d R e , where R d and R e 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 amidato (-NR f (COR g ), where R f and R gare 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), amidinato (-NR h C(NR i )R j , where R h , R i and Rj 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), alkylthio and arylthio (-SR k , where R k 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) or a thiocarboxyl group (-SCO)R l , R l 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; R 18 ~R 20 At least one of the groups is alkoxy and aryloxy (-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)Rc , R c 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 d R e , where R d and R e 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 amidato (-NR f (COR g ), where R f and R g 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), amidinato (-NR h C(NR i )R j , where R h , R i and R j 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 C1 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), alkylthio and arylthio (-SR k , where R kis 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) and a thiocarboxyl group (-S(CO)R l , R l is selected from hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.

[0066] The metal compound contained in the metal-containing resist composition is represented by the following Chemical Formula 5 or Chemical Formula 6. [ka] In the above Chemical Formula 5, R 21 is a C1 to C31 hydrocarbyl group, where 0 <z≦2であり、0<(z+x)≦4であり; [ka] In the above Chemical Formula 6, R 22 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 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof; M is tin (Sn) or antimony (Sb); X is sulfur (S), selenium (Se), or tellurium (Te); Y is -OR m or -OC(=O)R n and R mis a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R n 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; The p, q, l and k are independently integers of 1 to 20.

[0067] 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).

[0068] Subsequently, a first heat treatment step is performed in which the substrate on which the resist 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 this process, the solvent evaporates, and the resist film can be more firmly adhered to the substrate.

[0069] Furthermore, the resist film is selectively exposed to light.

[0070] Examples of light that can be used in the exposure process include light such as activating radiation i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), as well as light with high energy wavelengths such as EUV (Extreme Ultra Violet; wavelength 13.5 nm) and E-Beam (electron beam).

[0071] More specifically, the exposure light according to one embodiment may be light having a wavelength range of 5 nm to 150 nm, or may be light having a high-energy wavelength such as EUV (Extreme Ultra Violet; wavelength 13.5 nm) or E-Beam (electron beam).

[0072] In the step of forming the resist pattern, a negative type pattern may be formed.

[0073] The exposed regions of the photoresist film form polymers through crosslinking reactions such as condensation between organometallic compounds, resulting in different solubilities from the unexposed regions of the photoresist film.

[0074] Subsequently, the substrate is subjected to a second heat treatment step, which 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 resist film becomes less soluble in a developer.

[0075] Specifically, the resist film corresponding to the unexposed area is dissolved using an organic solvent such as 2-heptanone and then removed, thereby completing a photoresist pattern corresponding to the negative tone image.

[0076] The developer used in the pattern formation method according to one embodiment may be an organic solvent, and examples thereof include ketones such as methyl ethyl ketone, acetone, cyclohexanone, and 2-heptanone; alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, and methanol; esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, and butyrolactone; aromatic compounds such as benzene, xylene, and toluene; and combinations thereof.

[0077] In addition, the pattern formation method may further include a step of applying a composition for removing edge bead of a metal-containing resist after the exposure and development steps, 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).

[0078] As described above, photoresist patterns formed by exposure to light having wavelengths such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), as well as high-energy light such as EUV (Extreme Ultra Violet; wavelength 13.5 nm) and E-Beam (electron beam), can have a thickness range of 5 nm to 100 nm. For example, the photoresist patterns can be formed with thickness ranges 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, and 5 nm to 20 nm.

[0079] 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 pitch with a linewidth roughness of about 10 nm or less, about 5 nm or less, about 3 nm or less, or about 2 nm or less. [Example]

[0080] The present invention will be described in more detail below through examples of the preparation of the composition for removing edge bead of the metal-containing resist. However, the technical features of the present invention are not limited to the following examples.

[0081] Preparation Example: Preparation of Photoresist Composition Containing Organometallic Compound An organometallic compound having a structural unit of the following chemical formula C is 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]

[0082] Examples and Comparative Examples: Preparation of Edge Bead Removal Composition The alcohol compound and solvent are mixed according to the composition in Table 1 below, 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.

[0083] [Table 1]

[0084] *PGMEA; propylene glycol methyl ether acetate *PGME; propylene glycol methyl ether *MIBC: Methyl isobutyl carbinol *PEP:PGMEA:PGME=7:3(w / w) mixed solvent

[0085] Evaluation 1: Residual film thickness evaluation (Strip test) and Sn residual amount evaluation before development 1.0 mL of the organometallic compound-containing photoresist composition according to the Preparation Example was dispensed onto a 6-inch silicon wafer, left for 20 seconds, and then spin-coated at 800 rpm for 30 seconds. The wafer was then heat-treated at 200°C for 60 seconds, and the resulting resist film was measured for thickness using ellipsometry. 10 mL of each of the edge bead removal compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 5 was dispensed along the edge of the wafer, spin-coated for 5 seconds, and then dried by spinning at 1,500 rpm. The wafer was then heat-treated at 150°C for 60 seconds, and the resulting film was re-measured for thickness using ellipsometry to confirm the change in thickness before and after the edge bead removal process. The thickness was evaluated according to the following criteria. VPDICP-MS analysis was also performed to confirm the amount of residual Sn, and the results are shown in Table 2. *If the residual thickness is less than 5A: ○, if it is 5A or more: X

[0086] Evaluation 2: Visual evaluation of backside dirt The surface contamination of the wafer on which the resist film was formed after the edge bead removal process as in Evaluation 1 was checked using KMAC-ST400DLX equipment, and at the same time, the back surface contamination of the substrate was checked with the naked eye before and after the final bake at 150°C for 60 seconds. The notation criteria are as follows. *No stains before / after baking: ○, stains remain but disappear after baking: △, stains remain after baking: X

[0087] [Table 2]

[0088] Referring to Table 2, it can be seen that the compositions for removing edge bead of metal-containing resist according to the examples have a superior metal removal effect and can further promote the reduction of residual metal compared to the compositions for removing edge bead of metal-containing resist according to the comparative examples.

[0089] While specific embodiments of the present invention have been described and illustrated above, it will be apparent to those skilled in the art that the present invention is not limited to the described embodiments, and that various modifications and variations are possible without departing from the spirit and scope of the present invention. Therefore, such modifications or variations should not be understood separately from the technical spirit or perspective of the present invention, and the modified embodiments should be considered to fall within the scope of the claims of the present invention. [Explanation of symbols]

[0090] 1...substrate support, 2...spray nozzle, 10...photoresist solution, 12...edge bead, W...substrate.

Claims

1. organic solvents, at least one alcohol compound selected from diol compounds and cyclic alcohol compounds; and an acid compound having a pKa1 of 1.0≦pKa1≦4.5; 1. A composition for edge bead removal of metal-containing resists, comprising:

2. The composition for removing edge bead of metal-containing resist according to claim 1, wherein the diol compound is represented by the following Chemical Formula 1 or Chemical Formula 2: 【Chemistry 1】 In the above Chemical Formula 1 and Chemical Formula 2, R １ ~R １０ are each independently hydrogen, halogen, a hydroxy group, an amino group, a nitro group, a substituted or unsubstituted C1 to C30 amine group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group; R １ ~R ５ one of which is a hydroxy group, R ６ ~R １０ one of which is a hydroxy group, n is an integer from 1 to 10.

3. The formula 1 is represented by the following formula 1-1: The composition for removing edge bead of metal-containing resist according to claim 2, wherein the chemical formula 2 is represented by any one of the following chemical formulas 2-1 to 2-3: 【Chemistry 2】 【Transformation 3】 In the above Chemical Formula 1-1 and Chemical Formula 2-1 to Chemical Formula 2-3, R １ ~R ４ , R ６ ~R １０ and n is as defined in claim 2.

4. The composition for removing edge bead of metal-containing resist according to claim 1, wherein the cyclic alcohol compound is represented by the following chemical formula 3: 【Chemistry 4】 In the above Chemical Formula 3, R １１ ~R １６ are each independently hydrogen, halogen, a hydroxy group, an amino group, a nitro group, a substituted or unsubstituted C1 to C30 amine group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group; R １１ ~R １６ At least one of these is a hydroxy group.

5. The composition for removing edge bead of metal-containing resist according to claim 4, wherein the chemical formula 3 is represented by any one of the following chemical formulas 3-1 to 3-3: 【Transformation 5】 In Chemical Formula 3-1 to Chemical Formula 3-3, R １１ ~R １６ is as defined in claim 4.

6. 2. The composition for removing edge bead of metal-containing resist according to claim 1, wherein the alcohol-based compound is at least one of pyrocatechol, 4-methylcatechol, 4-chlorocatechol, 4-nitrocatechol, tropolone, and 1,2-ethanediol, or a combination thereof.

7. 2. The composition for removing edge bead of metal-containing resist according to claim 1, wherein the pKa1 of said acid compound is 1.0≦pKa1≦4.

0.

8. 2. The composition for removing edge bead of a metal-containing resist according to claim 1, wherein the acid compound is at least one of phosphoric acid, phosphonic acid, methylphosphonic acid, ethylphosphonic acid, butylphosphonic acid, hexylphosphonic acid, n-octylphosphonic acid, tetradecylphosphonic acid, octadecylphosphonic acid, phenylphosphonic acid, vinylphosphonic acid, 6-hydroxyhexylphosphonic acid, decylphosphonic acid, methylenediphosphonic acid, nitrilotrimethylenetriphosphonic acid, diphenylphosphinic acid, bis(4-methoxyphenyl)phosphinic acid, phosphinic acid, bis(hydroxymethyl)phosphinic acid, phenylphosphinic acid, p-(3-aminopropyl)-p-butylphosphinic acid, chloroacetic acid, formic acid, acetic acid, and combinations thereof.

9. 0.05 to 40% by weight of the alcohol compound and the acid compound; and 60 to 99.95% by weight of the organic solvent 2. The metal-containing resist edge bead removal composition of claim 1, comprising:

10. 2. The composition for removing edge bead of metal-containing resist according to claim 1, wherein the alcohol-based compound and the acid compound are contained in a weight ratio of 1:0.5 to 1:

50.

11. 2. The composition for removing edge bead of metal-containing resist according to claim 1, wherein the metal-containing resist contains a metal compound containing at least one of an organotin oxo group and an organotin carboxyl group.

12. The composition for removing edge bead of metal-containing resist according to claim 11, wherein the metal compound is represented by the following chemical formula 4: 【Transformation 6】 In the above Chemical Formula 4, R １７ is selected from 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, and a substituted or unsubstituted C7 to C30 arylalkyl group; R １８ ~R ２０ are each independently 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, alkoxy, and aryloxy (-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 ｃ , R ｃ 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 ｄ R ｅ , where R ｄ and R ｅ 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), amidate (—NR ｆ (COR ｇ ), where R ｆ and R ｇ 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), amidinato (—NR ｈ C (NR ｉ ) R ｊ , where R ｈ , R ｉ and Rj 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), alkylthio and arylthio (-SR ｋ , where R ｋ 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) or a thiocarboxyl group (—SCO)R ｌ , R ｌ 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; R １８ ~R ２０ At least one of the groups is alkoxy and aryloxy (—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 ｃ , R ｃ 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 ｄ R ｅ , where R ｄ and R ｅ 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), amidate (—NR ｆ (COR ｇ ), where R ｆ and R ｇ 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), amidinato (—NR ｈ C (NR ｉ ) R ｊ , where R ｈ , R ｉ and R ｊ 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 C 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), alkylthio and arylthio (-SR ｋ , where R ｋ 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), and a thiocarboxyl group (—S(CO)R ｌ , R ｌ is selected from 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.

13. The composition for removing edge bead of metal-containing resist according to claim 11, wherein the metal compound is represented by the following chemical formula 5 or 6: 【Transformation 7】 In the above Chemical Formula 5, R ２１ is a C1 to C31 hydrocarbyl group, where 0<z≦2 and 0<(z+x)≦4; 【Transformation 8】 In the above Chemical Formula 6, R ２２ 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 aliphatic unsaturated organic group containing one or more double or triple bonds, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof; M is tin (Sn) or antimony (Sb); X is sulfur (S), selenium (Se), or tellurium (Te); Y is -OR ｍ or -OC(=O)R ｎ and The R ｍ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R ｎ 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; The p, q, l and k are independently integers of 1 to 20.

14. 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 13 along the edge of the substrate; a heat treatment step of drying and heating to form a metal-containing resist film on the substrate; and A step of forming a resist pattern by exposure and development A pattern forming method comprising:

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