Composition for removing edge beads from metal-containing photoresists or developer composition for metal-containing photoresists, and pattern formation method using the same

Abstract

The present invention provides a composition for removing edge beads from metal-containing photoresists or a developer composition for metal-containing photoresists, and a pattern formation method using the same. [Solution] A cyclic compound comprising at least one heteroatom selected from N, O, and S in the ring and at least two carbonyl groups; and a solvent, comprising an edge bead removal composition for metal-containing photoresists or a developer composition for metal-containing photoresists.

Description

[Technical Field]

[0001] The present invention relates to a composition for removing edge beads from metal-containing photoresists or a developer composition for metal-containing photoresists, and a pattern forming 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 created a need for new types of high-performance photoresist materials and patterning methods to meet the demands for processing and patterning increasingly smaller features.

[0003] Furthermore, with the recent dramatic development of the semiconductor industry, there is a demand for faster operating speeds and larger storage capacities in semiconductor devices. To meet 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 direct circuits, which can be achieved through the photolithography process. That is, it has become important to consider integrating 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 the photoresist.

[0004] In particular, during the process of forming the photoresist layer, the resist is mainly applied to the silicon substrate while it is rotating. In this process, the resist is also applied to the edges and back surface of the substrate, which can cause pressure magnetization or pattern defects in subsequent semiconductor processes such as etching and ion implantation. Therefore, a process called EBR (EDGE BEAD REMOVAL) is performed to strip and remove the photoresist applied to the edges and back surface of the silicon substrate using a thinner composition. The EBR process requires a composition that exhibits excellent solubility for photoresist and effectively removes the beads and photoresist remaining on the substrate without generating resist residue.

[0005] Furthermore, there is a need to develop photoresists and developer compositions that can ensure excellent etching resistance and resolution in the photolithography process, while simultaneously improving sensitivity and CD (critical dimension) uniformity, and improving LER (line edge roughness) characteristics. [Overview of the project] [Problems that the invention aims to solve]

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

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

[0008] A composition for removing edge beads from metal-containing photoresists or a developer composition for metal-containing photoresists according to one embodiment comprises a cyclic compound containing at least one heteroatom selected from N, O, and S in the ring and at least two carbonyl groups; and a solvent.

[0009] A pattern formation method according to another embodiment includes the steps of: applying a metal-containing photoresist composition onto a substrate; applying the above-mentioned metal-containing photoresist edge bead removal composition along the edge of the substrate; a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate; an exposure step of the metal-containing photoresist film; and a development step.

[0010] Furthermore, a pattern formation method according to another embodiment includes the steps of: applying a metal-containing photoresist composition onto a substrate; a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate; exposing the metal-containing photoresist film; and developing it using the metal-containing photoresist developer composition described above.

[0011] Furthermore, a pattern formation method according to another embodiment includes the steps of: applying a metal-containing photoresist composition onto a substrate; applying the above-described metal-containing photoresist edge bead removal composition along the edge of the substrate; a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate; an exposure step of the metal-containing photoresist film; and a development step of using the above-described metal-containing photoresist developer composition. [Effects of the Invention]

[0012] A composition for removing edge beads from metal-containing photoresists according to one embodiment can satisfy the requirements for processing and patterning even smaller features by reducing metal substrate contamination inherent in the metal-containing photoresist and removing the resist applied to the edges and back surface of the substrate.

[0013] Another embodiment of the metal-containing developer composition minimizes defects present in the metal-containing photoresist film after the exposure process, enabling easy development and thereby achieving excellent contrast characteristics, superior sensitivity, and reduced line edge roughness (LER). [Brief explanation of the drawing]

[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. [Modes for carrying out the invention]

[0015] 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, descriptions of functions or configurations that have already been made public will be omitted.

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

[0017] In the drawings, thicknesses were enlarged to clearly represent various layers and regions. Furthermore, for explanatory purposes, the thicknesses of some layers and regions were exaggerated in the drawings. When a layer, film, region, plate, or other part is described as being "on top of" or "on" another part, this includes not only cases where it is "directly on top of" 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, halogen groups, hydroxyl groups, thiol groups, cyano groups, carbonyl groups, carboxyl groups, amino groups, amide groups, ester groups, substituted or unsubstituted C1-C30 amine groups, nitro groups, substituted or unsubstituted C1-C40 silyl groups, C1-C30 alkyl groups, C1-C10 haloalkyl groups, C1-C10 alkylsilyl groups, C3-C30 cycloalkyl groups, C6-C30 aryl groups, C1-C20 alkoxy groups, or C1-C20 sulfide groups. "Unsubstituted" means that the hydrogen atom is not substituted with other substituents and remains as a hydrogen atom.

[0019] In this document, "alkyl (alkyl) group" means a linear or branched aliphatic hydrocarbon group unless otherwise defined. The alkyl group may also be a "saturated alkyl group" that does not contain any double or triple bonds.

[0020] The alkyl group may be an alkyl group having 1 to 20 carbon atoms. More specifically, the alkyl group may be an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 6 carbon atoms. For example, an alkyl group having 1 to 5 carbon atoms 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, and tert-butyl.

[0021] The alkyl group mentioned above refers to, in specific examples, 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, a hexyl group, and so on.

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

[0023] 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 fused-ring polycyclic (i.e., rings sharing adjacent pairs of carbon atoms) functional groups.

[0024] More specifically, the substituted or unsubstituted C6-C30 aryl group may be, but is not limited to, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenantrenyl 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 benzophenantrenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perilennyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, or a combination thereof.

[0025] Figure 1 is a schematic diagram showing a photoresist coating apparatus.

[0026] 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.

[0027] The substrate support 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 1, and the injection nozzle 2 is located in a standby 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.

[0028] Specifically, in the coating process, the photoresist solution 10 is mainly applied by a spin coating method, and a predetermined amount of viscous photoresist solution 10 is supplied to the center of the substrate W and gradually spreads toward the periphery of the substrate by centrifugal force.

[0029] Therefore, the thickness of the photoresist is formed flat by the rotation speed of the substrate support.

[0030] However, as the solvent evaporates, the viscosity gradually increases, and due to the action of surface tension, a relatively large amount of photoresist bulges up at the periphery of the substrate. In more serious cases, the photoresist bulges up to the underside of the periphery of the substrate, which is called an edge bead 12.

[0031] The following describes a composition for removing edge beads from metal-containing photoresists or a developer composition for metal-containing photoresists according to one embodiment.

[0032] A composition for removing edge beads from metal-containing photoresists or a developer composition for metal-containing photoresists according to one embodiment of the present invention comprises a cyclic compound containing at least one heteroatom selected from N, O, and S in the ring and at least two carbonyl groups; and a solvent.

[0033] Since the electrons delocalized through the conjugation of at least one heteroatom selected from N, O, and S and a carbonyl group in the structure of the above-mentioned cyclic compound can move freely, it is advantageous to form a hydrogen bond with the side ligand of the metal-containing photoresist by including the cyclic compound, and it has the effect of inducing the desorption of the ligand. Therefore, the cyclic compound can effectively remove a metal by binding to the metal to form a metal-containing photoresist, more specifically, a metal residue, for example, a tin-based metal residue, and can improve the pattern forming property.

[0034] Specifically, the cyclic compound is represented by any one of the following Chemical Formulas 1 to 3.

[0035]

Chemical Formula

[0036] In the above Chemical Formulas 1 to 3, X 1 ~X 18 are each independently a carbonyl group (C=(O)), CR 1 R 2 , NR 3 , O or S, X 1 ~X 5 at least one of which is NR 3 , O or S, and at least two of which are carbonyl groups, X 6 ~X 11 at least one of which is NR 3 , O or S, and at least two of which are carbonyl groups, X 12 ~X 18 at least one of which is NR 3 , O or S, and at least two of which are carbonyl groups, R 1 ~R 3 are each independently hydrogen, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a combination thereof.

[0037] More specifically, the aforementioned chemical formula 1 is represented by the following chemical formula 1-1.

[0038] [ka]

[0039] In the above chemical formula 1-1, X 2 , X 4 and X 5 Each is independent of the other, CR 1 R 2 , NR 3 , O or S, X 2 , X 4 and X 5 At least one of them is NR 3 , O or S, R 1 ~R 3 Each of these is independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C1-C10 alkyl group, or a combination thereof.

[0040] For example, X 4 and X 5 At least one of them is NR 3 It can be O or S.

[0041] For example, X 4 and X 5 Each is independent of the other, NR 3 It can be O or S.

[0042] More specifically, the aforementioned chemical formula 2 is represented by one of the following chemical formulas 2-1 to 2-3.

[0043] [ka]

[0044] In the aforementioned chemical formula 2-1, X 7, X 9 , X 10 and X 11 Each is independent of the other, CR 1 R 2 , NR 3 , O or S, X 7 , X 9 , X 10 and X 11 At least one of them is NR 3 , O or S, R 1 ~R 3 Each of these is independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C1-C10 alkyl group, or a combination thereof.

[0045] For example, X 7 , X 9 and X 11 At least one of them is NR 3 It can be O or S.

[0046] For example, X 7 and X 11 At least one of them is NR 3 It can be O or S.

[0047] For example, X 9 and X 11 At least one of them is NR 3 It can be O or S.

[0048] For example, X 7 and X 9 Each is independent of the other, NR 3 It can be O or S.

[0049] [ka]

[0050] In the aforementioned chemical formula 2-2, X 7 , X 8 , X 10 and X11 is independently, CR 1 R 2 、NR 3 、O or S, and X 7 、X 8 、X 10 and X 11 at least one of which is NR 3 、O or S, and R 1 ~R 3 are each independently hydrogen, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a combination thereof.

[0051] For example, X 7 、X 8 and X 10 at least one of which may be NR 3 、O or S.

[0052] For example, X 7 and X 10 at least one of which may be NR 3 、O or S.

[0053] For example, X 7 and X 10 may each independently be NR 3 、O or S.

[0054]

Chemical formula

[0055] In the chemical formula 2-3 above, X 7 、X 9 and X 11 are each independently CR 1 R 2 、NR 3 、O or S, and X 7 、X 9 and X[[ID=9D]] 11 at least one of which is NR 3, O or S, and R 1 ~R 3 are each independently hydrogen, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a combination thereof.

[0056] For example, X 7 and X 11 can each independently be NR 3 , O or S.

[0057] For example, X 7 , X 9 and X 11 can each independently be NR 3 , O or S.

[0058] More specifically, the chemical formula 3 is represented by any one of the following chemical formulas 3-1 to 3-3.

[0059] [Chemical formula]

[0060] In the chemical formula 3-1, X 12 , X 13 , X 15 , X 17 and X 18 are each independently CR 1 R 2 , NR 3 , O or S, and X 12 , X 13 , X 15 , and X 17 ~X 18 at least one of which is NR 3 , O or S, and R 1 ~R 3 are each independently hydrogen, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a combination thereof.

[0061] For example, X 12 , X 13 , X 15 , X 17 and X 18 Two of them are independent of each other, NR 3 It can be O or S.

[0062] For example, X 12 , X 13 , X 15 , X 17 and X 18 Three of them are independent of each other, NR 3 It can be O or S.

[0063] For example, X 12 , X 13 , X 15 , X 17 and X 18 Four of them are independent of each other, NR 3 It can be O or S.

[0064] For example, X 12 , X 13 , X 15 and X 17 Each is independent of the other, NR 3 It can be O or S.

[0065] [ka]

[0066] In the aforementioned chemical formula 3-2, X 12 , X 13 , X 15 , X 16 and X 18 Each is independent of the other, CR 1 R 2 , NR 3 , O or S, X 12 , X 13 , X 15 , X 16 and X 18 At least one of them is NR 3, O or S, R 1 ~R 3 Each of these is independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C1-C10 alkyl group, or a combination thereof.

[0067] For example, X 12 , X 13 , X 15 , X 16 and X 18 Two of them are independent of each other, NR 3 It can be O or S.

[0068] For example, X 12 , X 13 , X 15 , X 16 and X 18 Three of them are independent of each other, NR 3 It can be O or S.

[0069] For example, X 12 , X 13 , X 15 , X 16 and X 18 Four of them are independent of each other, NR 3 It can be O or S.

[0070] For example, X 13 , X 15 , X 16 and X 18 Each is independent of the other, NR 3 It can be O or S.

[0071] [ka]

[0072] In the aforementioned chemical formula 3-3, X 13 , X 15 , X 16 and X 18 Each is independent of the other, CR 1 R 2 , NR3 , O or S, X 13 , X 15 , X 16 and X 18 At least one of them is NR 3 , O or S, R 1 ~R 3 Each of these is independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C1-C10 alkyl group, or a combination thereof.

[0073] For example, X 13 , X 15 , X 16 and X 18 Two of them are independent of each other, NR 3 It can be O or S.

[0074] For example, X 13 , X 15 , X 16 and X 18 Three of them are independent of each other, NR 3 It can be O or S.

[0075] For example, X 13 , X 15 , X 16 and X 18 Each is independent of the other, NR 3 It can be O or S.

[0076] In one embodiment, the cyclic compound may be at least one selected from the compounds listed in Group 1 below.

[0077] [ka]

[0078] In one embodiment, the cyclic compound may be present in an amount of 0.1 to 50% by weight based on the total weight of the composition.

[0079] For example, the cyclic compound may be present in an amount of 0.1 to 40% by weight or 0.5 to 40% by weight based on the total weight of the composition.

[0080] As an example of a solvent contained in a metal-containing photoresist edge bead removal composition or developer composition according to one embodiment, deionized water (DIW), 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), diene butyl ether (DBE), diisopropyl ether (DIAE), acetylacetone, butyl lactate (n-Butyllactate), 4-methyl-2-pentanol (or methyl isobutyl Carbinol (MIBC) can be written as, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl ethyl acetate, ethyl acetate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, Examples include, but are not limited to, methyl methoxypropionate, ethyl ethoxypropionate, or mixtures thereof.

[0081] The metal-containing photoresist edge bead removal composition according to the present invention may be particularly effective in removing metal-containing photoresists, and more specifically, undesirable metal residues, such as tin substrate metal residues.

[0082] Furthermore, the metal-containing photoresist developer composition according to the present invention can achieve excellent pattern characteristics by minimizing defects present in the metal-containing photoresist film after the exposure process and facilitating easy development.

[0083] Furthermore, it can achieve excellent sensitivity and reduced line edge roughness (LER).

[0084] If other additives described later are included, the solvent may be present in the amount remaining after deducting the components that are included.

[0085] The product may further contain at least one other additive selected from surfactants, dispersants, hygroscopic agents, and coupling agents.

[0086] The metal compound contained in the metal-containing photoresist may be an organotin compound containing at least one of an organic oxy group and an organic carbonyl oxy group.

[0087] As an example, the metal compound contained in the metal-containing photoresist is represented by the following chemical formula 4.

[0088] [ka]

[0089] In the aforementioned chemical formula 4, R 4 This is selected from 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, and substituted or unsubstituted C6-C30 arylalkyl groups. R 5 ~R 7Each of these independently comprises 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 C6-C30 arylalkyl group, an alkoxy, and an aryloxy (-OR) group. a , here R a (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 b , R b (where 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 c R d , here R c and R d 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), amidato (-NR e (COR f ), here R e and R fEach 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), amidinato (-NR g C(NR h )R i , here R g , R h , and R i 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), alkylthio and arylthio (-SR j , here R j (wherein 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), or a thiocarboxyl group (-S(CO)R k , R k (These are hydrogen, 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.) R 5 ~R 7 At least one of them is an alkoxy and an aryloxy (-OR a , here R a(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 b , R b (where 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 c R d , here R c and R d 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), amidato (-NR e (COR f ), here R e and R f 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), amidinato (-NR g C(NR h )R i , here R g , R h , and R iEach 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), alkylthio and arylthio (-SR j , here R j (wherein 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), or a thiocarboxyl group (-S(CO)R k , R k (The group is selected from 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.)

[0090] As another example, the metal compound contained in the metal-containing photoresist is represented by the following chemical formula 5 or chemical formula 6. [ka] In the aforementioned chemical formula 5, R 8 is a hydrocarbyl group having 1 to 31 carbon atoms, where 0 <z≦2であり、0<(z+x)≦4であり; [ka] In the aforementioned chemical formula 6, R 9These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 aliphatic unsaturated organic groups containing one or more double or triple bonds, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C4-C30 heteroaryl groups, carbonyl groups, ethylene oxide groups, propylene oxide groups, or combinations thereof. X is sulfur (S), selenium (Se), or tellurium (Te). Y is -OR m Or -OC(=O)R n And, The aforementioned R m 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. R n These are hydrogen, 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. The aforementioned n, m, l, and k are independent integers between 1 and 20.

[0091] On the other hand, according to another embodiment, a pattern forming method can be provided that includes the step of removing edge beads using the above-described composition. For example, the manufactured pattern may be a photoresist pattern. More specifically, it may be a negative-type photoresist pattern.

[0092] A pattern formation method according to one embodiment includes the steps of: applying a metal-containing photoresist composition onto a substrate; applying the above-mentioned metal-containing photoresist edge bead removal composition along the edge of the substrate; a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate; an exposure step of the metal-containing photoresist film; and a development step.

[0093] More specifically, the step of forming a pattern using a metal-containing photoresist composition may include the steps of applying the metal-containing photoresist 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 photoresist composition to form a photoresist film. The metal-containing photoresist 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.

[0094] More specifically, the edge beads of the metal-containing photoresist can be removed by applying an appropriate amount of the aforementioned metal-containing photoresist 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).

[0095] 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 approximately 80°C to approximately 120°C, during which the solvent evaporates and the photoresist film can adhere more firmly to the substrate.

[0096] Then, the photoresist film is selectively exposed.

[0097] As an example, examples of light that can be used in the exposure process include not only short-wavelength light such as the activation irradiation diagram i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), but also high-energy wavelength light such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0098] More specifically, the exposure light in one embodiment may be light having a wavelength range of 5 nm to 150 nm, or it may be light having a wavelength range such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0099] During the process of forming the photoresist pattern, a negative type pattern can be formed.

[0100] The exposed regions within the photoresist film will have different solubility from the unexposed regions due to the formation of polymers through crosslinking reactions such as condensation between organometallic compounds.

[0101] 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 areas of the photoresist film become less soluble in the developer solution.

[0102] Specifically, the photoresist pattern corresponding to the negative tone image is completed by dissolving the photoresist film corresponding to the unexposed region using a solvent such as 2-heptanone, and then removing it.

[0103] Examples of solvents contained in the developer composition used in the pattern formation method according to one embodiment 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.

[0104] As described 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 thicknesses 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.

[0105] On the other hand, the photoresist pattern can 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.

[0106] A pattern formation method according to another embodiment includes the steps of: applying a metal-containing photoresist composition onto a substrate; a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate; exposing the metal-containing photoresist film; and developing it using the composition described above.

[0107] The step of applying the metal-containing photoresist composition onto the substrate is as described above.

[0108] The heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate is as described above.

[0109] The step of exposing the metal-containing photoresist film is as described above.

[0110] By dissolving and then removing the photoresist film corresponding to the unexposed region using the metal-containing photoresist developer composition described above, the photoresist pattern corresponding to the negative tone image is completed.

[0111] Specific examples of metal compounds included in the aforementioned metal-containing photoresist composition are as described above.

[0112] The following explains in detail how to develop and form patterns, using diagrams as examples.

[0113] Figure 2 is a cross-sectional view showing the process sequence to illustrate the pattern formation method.

[0114] Referring to Figure 2(a), the exposed photoresist film is developed to form the photoresist pattern 130P.

[0115] In an exemplary embodiment, an exposed photoresist film can be developed to remove 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.

[0116] In an 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.

[0117] Referring to Figure 2(b), the feature layer 110 is processed using the photoresist pattern 130P with the result of (a).

[0118] 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 2(b) illustrates an example of a process for processing the feature layer 110, where the feature layer 110 exposed through the opening OP is etched to form the feature pattern 110P.

[0119] Referring to Figure 2(c), the photoresist pattern 130P remaining on the feature pattern 110P in the result of (b) is removed. Ashing and stripping processes can be used to remove the photoresist pattern 130P. The feature pattern 110P is on the substrate 100.

[0120] Furthermore, a pattern formation method according to another embodiment includes the steps of: applying a metal-containing photoresist composition onto a substrate; applying the above-mentioned metal-containing photoresist edge bead removal composition along the edge of the substrate; a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate; an exposure step of the metal-containing photoresist film; and a development step of using the above-mentioned metal-containing photoresist developer composition.

[0121] The specific methods for each stage are as described above. By simultaneously using the edge bead removal composition for metal-containing photoresist or the developer composition for metal-containing photoresist 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 can be effectively improved, further satisfying the requirements for processing and patterning of small features, and achieving excellent contrast characteristics, excellent sensitivity, and reduced line edge roughness (LER). [Examples]

[0122] The present invention will be described in more detail below through examples relating to the production of the metal-containing photoresist edge bead removal composition and the metal-containing photoresist developer composition described above. However, the technical features of the present invention are not limited by the following examples.

[0123] Composition for removing edge beads from metal-containing photoresists Example 1 The cyclic compound and solvent were mixed according to the composition shown in Table 1 below, and then shaken at room temperature (25°C) to completely dissolve. The mixture was then passed through a PTFE filter with a pore size of 1 μm to obtain the final composition.

[0124] Examples 2 to 5 and Comparative Examples 1 to 5 The composition was obtained in the same manner as in Example 1, except that the composition was changed to that shown in Table 1 below.

[0125] [Table 1]

[0126] [ka]

[0127] [ka]

[0128] Manufacturing of developer compositions for metal-containing photoresists Example 7 The polyphenol compound and solvent were mixed according to the compositions shown in Table 2 below, and then shaken at room temperature (25°C) to completely dissolve them. The mixture was then passed through a PTFE filter with a pore size of 1 μm to obtain the final composition.

[0129] Examples 8 to 11 and Comparative Examples 6 to 10 The composition was obtained in the same manner as in Example 7, except that the composition was changed as shown in Table 2 below.

[0130] [Table 2]

[0131] Manufacturing of organometallic photoresist compositions Manufacturing example An organometallic compound having the structural unit of chemical formula C shown below (weight-average molecular weight: 1,500 g / mol) 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.

[0132] [ka]

[0133] Evaluation 1: Sn residue level evaluation 1.0 mL of the organometallic compound-containing photoresist composition according to the above manufacturing example was placed on a 6-inch silicon wafer, allowed to stand for 20 seconds, and then spin-coated at a speed of 800 rpm for 30 seconds. The thickness of the resulting coating film was then measured using ellipsometry after heat treatment at 200°C for 60 seconds. 10 mL each of the edge bead removal compositions from Examples 1 to 7 and Comparative Examples 1 to 12, as shown in Table 1, were placed along the edge of the wafer with the resist film formed on it, and after spin-coating for 5 seconds, the wafer was rotated at a speed of 1,500 rpm to dry. The film quality was then heat-treated at 150°C for 60 seconds, and VPD ICP-MS analysis was performed to confirm the amount of residual Sn. The results are shown in Table 3.

[0134] [Table 3]

[0135] Referring to Table 3, it can be confirmed that the metal-containing photoresist edge bead removal composition according to the example is superior in metal removal effect compared to the metal-containing photoresist edge bead removal composition according to the comparative example, and can further promote the reduction of residual metal.

[0136] Evaluation 2: ArF pattern evaluation The organometallic photoresist (PR) composition prepared as described above was spin-coated onto an 8-inch wafer at 1,500 rpm for 30 seconds, and then heat-treated at 110°C for 60 seconds to produce a coated wafer.

[0137] This was exposed to light in an L / S pattern at 20-35 mJ using an ArF immersion lithography apparatus (manufactured by Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35-degree dipole s-polarized illumination, 6% halftone phase-shift mask), then baked (PEB) at 100°C for 60 seconds. The developer compositions obtained from Examples 7-12 and Comparative Examples 6-10 were applied, and a development process was carried out at 1500 rpm spin for 30 seconds. Finally, it was cured at 240°C for 60 seconds to obtain a 40 nm 1:1 line-and-space pattern. The cross-sectional shape of this pattern was observed using an electron microscope. The ArF pattern performance was evaluated by the pattern collapse rate calculated by the following formula 1 among the generated patterns. [Formula 1] Pattern collapse rate = {(Number of collapsed patterns) / (Total number of patterns)} * 100 (%)

[0138] [Evaluation Criteria] ○: Pattern breakdown occurrence rate <60% X: Pattern collapse occurrence rate ≥ 60%

[0139] [Table 4]

[0140] Referring to Table 4, it can be confirmed that when the metal-containing photoresist developer composition according to the examples is applied, superior resolution and minimized pattern breakdown are achieved compared to when the metal-containing photoresist developer composition according to the comparative examples is applied.

[0141] Although specific embodiments of the present invention have been described and illustrated above, it is obvious to those with 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 present invention, and the modified embodiments should be considered to fall within the scope of the claims of the present invention. [Explanation of Symbols]

[0142] 1...Substrate support part, 2...Injection nozzle, 10...Photoresist solution, 12...Edge bead, 100...Substrate, OP...Opening, 110...Feature layer, 110P...Feature pattern, 130P...Photoresist pattern.

Claims

1. A composition for removing edge beads from metal-containing photoresists or a developer composition for metal-containing photoresists, comprising a cyclic compound containing at least one heteroatom selected from N, O, and S in the ring and at least two carbonyl groups; and a solvent.

2. The cyclic compound is represented by any one of the following chemical formulas 1 to 3, and is the metal-containing photoresist edge bead removal composition or metal-containing photoresist developer composition according to claim 1: 【Chemistry 1】 In the aforementioned chemical formulas 1 to 3, X １ ~X １８ Each is independently a carbonyl group (C=(O)), CR １ R ２ , NR ３ , O or S, X １ ~X ５ At least one of them is NR ３ , O or S, and at least two are carbonyl groups, X ６ ~X １１ At least one of which is NR ３ , O or S, and at least two are carbonyl groups, X １２ ~X １８ At least one of them is NR ３ , O or S, and at least two are carbonyl groups, R １ ~R ３ Each of these is independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C1-C10 alkyl group, or a combination thereof.

3. The aforementioned chemical formula 1 is represented by the following chemical formula 1-1, and is the metal-containing photoresist edge bead removal composition or metal-containing photoresist developer composition according to claim 2: 【Chemistry 2】 In the aforementioned chemical formula 1-1, X ２ , X ４ and X ５ Each is independent of CR １ R ２ , NR ３ , O or S, X ２ , X ４ and X ５ At least one of them is NR ３ , O or S, R １ ~R ３ Each of these is independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C1-C10 alkyl group, or a combination thereof.

4. The aforementioned chemical formula 2 is represented by any one of the following chemical formulas 2-1 to 2-3, and is the metal-containing photoresist edge bead removal composition or metal-containing photoresist developer composition according to claim 2: 【Transformation 3】 In the aforementioned chemical formula 2-1, X ７ , X ９ , X １０ and X １１ Each is independent of CR １ R ２ , NR ３ , O or S, X ７ , X ９ , X １０ and X １１ At least one of them is NR ３ , O or S, R １ ~R ３ Each of these is independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C1-C10 alkyl group, or a combination thereof; In the aforementioned chemical formula 2-2, X ７ , X ８ , X １０ and X １１ Each is independent of CR １ R ２ , NR ３ , O or S, X ７ , X ８ , X １０ and X １１ At least one of them is NR ３ , O or S, R １ ~R ３ Each of these is independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C1-C10 alkyl group, or a combination thereof; In the above chemical formula 2-3, X ７ , X ９ and X １１ Each is independent of CR １ R ２ , NR ３ , O or S, X ７ , X ９ and X １１ At least one of them is NR ３ , O or S, R １ ~R ３ Each of these is independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C1-C10 alkyl group, or a combination thereof.

5. The aforementioned chemical formula 3 is represented by any one of the following chemical formulas 3-1 to 3-3, and is the metal-containing photoresist edge bead removal composition or metal-containing photoresist developer composition according to claim 2: 【Chemistry 4】 In the aforementioned chemical formula 3-1, X １２ , X １３ , X １５ , X １７ and X １８ Each is independent of CR １ R ２ , NR ３ , O or S, X １２ , X １３ , X １５ , and X １７ ~X １８ At least one of them is NR ３ , O or S, R １ ~R ３ Each of these is independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C1-C10 alkyl group, or a combination thereof; In the aforementioned chemical formula 3-2, X １２ 、 X １３ 、 X １５ 、 X １６ 以及 X １８ 各自独立地为 CR １ R ２ 、 NR ３ 、 O 或 S, X １２ , X １３ , X １５ , X １６ and X １８ at least one of which is NR ３ , O or S, R １ ~R ３ Each of these is independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C1-C10 alkyl group, or a combination thereof; In the aforementioned chemical formula 3-3, X １３ , X １５ , X １６ and X １８ Each is independent of CR １ R ２ , NR ３ , O or S, X １３ , X １５ , X １６ and X １８ At least one of them is NR ３ , O or S, R １ ~R ３ Each of these is independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C1-C10 alkyl group, or a combination thereof.

6. The cyclic compound is at least one selected from the compounds listed in Group 1 below, according to claim 1, for the edge bead removal composition for metal-containing photoresists or the developer composition for metal-containing photoresists: 【Transformation 5】

7. The cyclic compound is present in an amount of 0.1 to 50% by weight based on the total weight of the composition, wherein the metal-containing photoresist edge bead removal composition or metal-containing photoresist developer composition is as described in claim 1.

8. The metal compound contained in the metal-containing photoresist is an organotin compound containing at least one of an organic oxy group and an organic carbonyl oxy group, as described in claim 1, for removing edge beads from a metal-containing photoresist or a developer solution composition for a metal-containing photoresist.

9. The metal compound contained in the metal-containing photoresist is represented by the following chemical formula 4, and is the edge bead removal composition for the metal-containing photoresist or the developer composition for the metal-containing photoresist according to claim 8: 【Transformation 6】 In the aforementioned chemical formula 4, R ４ This is selected from 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, and substituted or unsubstituted C6-C30 arylalkyl groups. R ５ ~R ７ Each of these independently comprises 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 C6-C30 arylalkyl group, an alkoxy and an aryloxy (-OR ａ Here, R ａ (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 ｂ , R ｂ (These are hydrogen, 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), alkylamides or dialkylamides (-NR ｃ R ｄ Here, R ｃ and R ｄ 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), amidato (-NR ｅ (COR ｆ ), here R ｅ and R ｆ 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), amidinato (-NR ｇ C (NR ｈ ) R ｉ Here, R ｇ , R ｈ , and R ｉ 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), alkylthio and arylthio (-SR ｊ Here, R ｊ (wherein 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), or a thiocarboxyl group (-S(CO)R ｋ , R ｋ (These are hydrogen, 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.) R ５ ~R ７ At least one of them is an alkoxy and an aryloxy (-OR ａ Here, R ａ (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 ｂ , R ｂ (These are hydrogen, 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), alkylamides or dialkylamides (-NR ｃ R ｄ Here, R ｃ and R ｄ 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), amidato (-NR ｅ (COR ｆ ), here R ｅ and R ｆ 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), amidinato (-NR ｇ C (NR ｈ ) R ｉ Here, R ｇ , R ｈ , and R ｉ 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), alkylthio and arylthio (-SR ｊ Here, R ｊ (wherein 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), or a thiocarboxyl group (-S(CO)R ｋ , R ｋ (The carbon atom is selected from 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.)

10. The metal compound contained in the metal-containing photoresist is represented by the following chemical formula 5 or chemical formula 6, and is the edge bead removal composition for the metal-containing photoresist or the developer composition for the metal-containing photoresist according to claim 8: 【Transformation 7】 In the aforementioned chemical formula 5, R ８ is a hydrocarbyl group having 1 to 31 carbon atoms, where 0 < z ≤ 2 and 0 < (z + x) ≤ 4; 【Transformation 8】 In the aforementioned chemical formula 6, R ９ These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 aliphatic unsaturated organic groups containing one or more double or triple bonds, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C4-C30 heteroaryl groups, carbonyl groups, ethylene oxide groups, propylene oxide groups, or combinations thereof. X is sulfur (S), selenium (Se), or tellurium (Te), Y is -OR ｍ or -OC(=O)R ｎ And, The aforementioned R ｍ 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. R ｎ These are hydrogen, 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. The aforementioned n, m, l, and k are independent integers between 1 and 20.

11. The steps include: applying a metal-containing photoresist composition onto a substrate, The steps include applying the metal-containing photoresist edge bead removal composition according to any one of claims 1 to 10 along the edge of the substrate, A heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate, The steps include: exposing the metal-containing photoresist film, A pattern formation method, including the development step.

12. The steps include: applying a metal-containing photoresist composition onto a substrate, A heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate, The steps include: exposing the metal-containing photoresist film, A method for forming a pattern, comprising the step of developing a metal-containing photoresist using a developing solution composition according to any one of claims 1 to 10.

13. The steps include: applying a metal-containing photoresist composition onto a substrate, The steps include applying the metal-containing photoresist edge bead removal composition according to any one of claims 1 to 10 along the edge of the substrate, A heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate, The steps include: exposing the metal-containing photoresist film, A method for forming a pattern, comprising the step of developing a metal-containing photoresist using a developing solution composition according to any one of claims 1 to 10.

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