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

Abstract

The present invention provides a composition for removing edge beads from metal-containing resists or a developer composition for metal-containing resists, and a pattern formation method using the same. [Solution] A composition for removing edge beads from metal-containing resists or a developer composition for metal-containing resists, comprising a polyphenol compound and an organic solvent, wherein the polyphenol compound is present in an amount of 10 to 50% by weight relative to 100% by weight of the entire composition, and a method for forming a pattern using the same are provided.

Description

[Technical Field]

[0001] This description relates to a composition for removing edge beads from metal-containing resists or a developer composition for metal-containing resists, and a method for forming patterns using the same. [Background technology]

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

[0003] Furthermore, 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 photoresist onto the substrate, selectively exposing it by irradiating it with ultraviolet light (including extreme ultraviolet light), electron beams, or X-rays, and then developing the photoresist.

[0004] In particular, in the process of forming a photoresist layer, the resist is mainly applied onto the silicon substrate while rotating the silicon substrate. During this process, the resist is also applied to the substrate edge and the back surface, which may cause piezomagnetism or pattern defects in subsequent semiconductor processes such as etching and ion implantation processes. Therefore, a process of stripping and removing the photoresist applied to the edge and the back surface of the silicon substrate using a thinner composition, that is, an EBR (EDGE BEAD REMOVAL) process, is carried out. In the EBR process, a composition that exhibits excellent solubility in the photoresist and effectively removes the beads and photoresist remaining on the substrate without generating resist residues is required.

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

Summary of the Invention

Problems to be Solved by the Invention

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

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

Means for Solving the Problems

[0008] The composition for removing edge beads of a metal-containing resist or the developer composition for a metal-containing resist according to one embodiment contains a polyphenol-based compound; and an organic solvent, and the polyphenol-based compound is contained at 10 to 50% by weight based on 100% by weight of the entire composition.

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

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

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

Advantages of the Invention

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

[0013] The metal-containing developer composition according to another embodiment can achieve excellent contrast characteristics, excellent sensitivity, and reduced line edge roughness (LER) by minimizing the defects present in the metal-containing photoresist film after the exposure process and making it easily developable.

Brief Description of the Drawings

[0014] [Figure 1] This is a schematic diagram showing a photoresist coating apparatus. [Figure 2] This is a cross-sectional view showing the process sequence to illustrate the pattern formation method. [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 provided arbitrarily 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 said to be "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 a hydrogen atom is substituted with deuterium, a halogen group, a hydroxyl 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-C40 silyl group, a C1-C30 alkyl group, a C1-C10 haloalkyl group, a C1-C10 alkylsilyl group, a C3-C30 cycloalkyl group, a C6-C30 aryl group, a C1-C20 alkoxy group, or a C1-C20 sulfide group. "Unsubstituted" means that a hydrogen atom remains as a hydrogen atom without being substituted by another substituent.

[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, to give specific examples, a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, and so on.

[0022] In the chemical formulas described herein, t-Bu represents a 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 fusion-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 perilenyl 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, etc.

[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 initially positioned in a standby area away from the top of the substrate W before moving to the top of the substrate during the solution supply stage 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 edges of the substrate W by the centrifugal force, and a portion of it moves to the side surface of the substrate and the underside of the edges 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 towards the edge 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 and the viscosity gradually increases, a relatively large amount of photoresist accumulates at the edges of the substrate due to the action of surface tension, and in more serious cases, the photoresist accumulates even on the underside of the substrate edge, which is called an edge bead 12.

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

[0032] A composition for removing edge beads from metal-containing resists or a developer solution composition for metal-containing resists according to one embodiment of the present invention comprises a polyphenol compound and an organic solvent, wherein the polyphenol compound is present in an amount of 10 to 50% by weight based on 100% by weight of the entire composition.

[0033] The inclusion of polyphenol compounds facilitates the direct formation of hydrogen bonds with the ligands of the metal compounds contained in the metal-containing resist, providing both acceptors and donors simultaneously. As a result, the polyphenol compounds can bind to the metal and effectively remove the metal-containing resist, and more specifically, metal residues, such as tin-based metal residues, thereby improving pattern formation.

[0034] In particular, polyphenol compounds have a structure in which acceptor and donor are conjugated, and electrons are delocalized and can move freely, which may further favor hydrogen bond formation.

[0035] Specifically, the polyphenol compound may be present in an amount of 10 to 40% by weight relative to 100% by weight of the entire composition.

[0036] More specifically, the polyphenol compound may be present in an amount of 10 to 30% by weight relative to 100% by weight of the entire composition.

[0037] As an example, the polyphenol compound may further contain at least one carbonyl group.

[0038] In one embodiment, the polyphenol compound may be at least one selected from the group consisting of tannic acid, ellagic acid, chrysophanol, usnic acid, quercetin, and resveratrol.

[0039] As an example of an organic solvent contained in a composition for removing edge beads from metal-containing resists or a developer solution composition according to one embodiment, propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), propylene glycol butyl ether (PGBE), ethylene glycol methyl ether, diethyl glycol ethyl methyl ether, dipropyl glycol dimethyl ether, ethanol, 2-butoxyethanol, n-propanol, isopropanol, n-butanol, isobutyl alcohol, hexanol, ethylene glycol, propylene glycol, heptanone, propylene carbonate, butylene carbonate, diethyl ether, dibutyl ether, ethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diisopentyl ether, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, acetonitrile, diacetone alcohol, 3,3-Dimethyl-2-butanone, N-methyl-2-pyrrolidone, dimethylacetamide, cyclohexanone methyl-2-hydroxy-2-methylpropanoate (HBM), γ-butyrolactone (GBL), 1-butanol (n-Butanol), ethyl lactate (EL), diene butyl ether (DBE), diisopropyl ether (DIAE), acetylacetone, butyl lactate (n-Butylactate), 4-methyl-2-pentanol (or methyl isobutyl Carbinol (can be written as MIBC), 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, butyl acetate, ethyl lactate, butyl lactate, methyl-2-hydroxyisobutyrate Examples include, but are not limited to, 2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, or mixtures thereof.

[0040] The metal-containing resist edge bead removal composition according to the present invention may be particularly effective in removing metal-containing resists, and more specifically, undesirable metal residues, such as tin substrate metal residues.

[0041] Furthermore, the metal-containing resist developer composition according to the present invention minimizes defects present in the metal-containing photoresist film after the exposure process, enabling easy development and thereby achieving excellent pattern characteristics.

[0042] In addition, it can also achieve excellent sensitivity and reduced line edge roughness (LER).

[0043] If other additives described later are included, the organic solvent may be included in the remaining amount after deducting the components that are included.

[0044] The product may further contain at least one other additive selected from surfactants, dispersants, hygroscopic agents, and coupling agents.

[0045] The metal compound contained in the metal-containing resist may be an organotin compound containing at least one of an organic oxy group and an organic carbonyl oxy group.

[0046] As an example, the metal compound contained in the metal-containing resist can be represented by the following chemical formula 1.

[0047] [ka]

[0048] In the above chemical formula 1, R 1 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 2 ~R 4are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, alkoxy and aryloxy (-OR a where R a is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), a carboxyl group (-O(CO)R b where R b is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), an alkylamide or dialkylamide (-NR c R d where R c and R d are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), an amidato (-NR e (COR f ) where R e and R fEach 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), 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 2 ~R 4 At least one of them is an alkoxy and an aryloxy (-OR a , here R a(which 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), a carboxyl group (-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 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), 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.)

[0049] As another example, the metal compound contained in the metal-containing resist can be represented by the following chemical formula 2 or chemical formula 3.

[0050] [ka] In the above chemical formula 2, R 5 These are hydrocarbyl groups with 1 to 31 carbon atoms, where 0 <z≦2であり、0<(z+x)≦4であり; [ka] In the above chemical formula 3, R 6These 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.

[0051] 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 aforementioned composition. For example, the manufactured pattern may be a photoresist pattern. More specifically, it may be a negative-type photoresist pattern.

[0052] A pattern formation method according to one embodiment includes the steps of: applying a metal-containing resist composition onto a substrate; applying the aforementioned metal-containing resist edge bead removal composition along the edge of the substrate; a heat treatment step of drying and heating to form a metal-containing resist film on the substrate; exposing the metal-containing photoresist film; and developing.

[0053] More specifically, the step of forming a pattern using a metal-containing resist composition may include the steps of applying the metal-containing resist composition onto a substrate on which a thin film has been formed by spin coating, slit coating, inkjet printing, etc., and drying the applied metal-containing resist composition to form a photoresist film. The metal-containing resist composition may contain a tin-based compound, for example, the tin-based compound may contain at least one of an organic oxy group-containing tin compound and an organic carbonyl oxy group-containing tin compound.

[0054] More specifically, the edge beads of the metal-containing resist can be removed by applying an appropriate amount of the aforementioned metal-containing resist edge bead removal composition along the edge of the substrate while rotating (spinning) the substrate at an appropriate speed (e.g., 500 rpm or more).

[0055] 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.

[0056] Then, the photoresist film is selectively exposed.

[0057] 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).

[0058] 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).

[0059] During the process of forming the photoresist pattern, a negative-type pattern can be formed.

[0060] The exposed regions in the photoresist film develop different solubility from the unexposed regions of the photoresist film by forming polymers through crosslinking reactions such as condensation between organometallic compounds.

[0061] Next, a second heat treatment step is performed on the substrate. This second heat treatment step can be carried out at a temperature of approximately 90°C to approximately 200°C. By performing this second heat treatment step, the exposed area of ​​the photoresist film becomes less susceptible to dissolution in the developer solution.

[0062] Specifically, by dissolving the photoresist film corresponding to the unexposed region using an organic solvent such as 2-heptanone, and then removing it, the photoresist pattern corresponding to the negative tone image can be completed.

[0063] Examples of organic solvents contained in the developer solution 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.

[0064] As mentioned above, photoresist patterns formed by exposure with light having wavelengths such as i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm), and ArF excimer laser (wavelength 193nm), as well as high-energy light such as EUV (Extreme UltraViolet; wavelength 13.5nm) and E-Beam (electron beam), can have a width of thickness from 5nm to 100nm. 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.

[0065] On the other hand, the photoresist pattern may have a half-pitch of approximately 50 nm or less, for example 40 nm or less, for example 30 nm or less, for example 20 nm or less, for example 15 nm or less, and a pitch having a line width roughness of approximately 10 nm or less, approximately 5 nm or less, approximately 3 nm or less, or approximately 2 nm or less.

[0066] A pattern formation method according to another embodiment includes the steps of applying a metal-containing resist composition onto a substrate, a heat treatment step of drying and heating to form a metal-containing resist film on the substrate, an exposure step of the metal-containing photoresist film, and a development step of using the aforementioned composition.

[0067] The step of applying the metal-containing resist composition onto the substrate is as described above.

[0068] The heat treatment step of drying and heating to form a metal-containing resist film on the substrate is as described above.

[0069] The step of exposing the metal-containing photoresist film is as described above.

[0070] By dissolving the photoresist film corresponding to the unexposed region using the aforementioned metal-containing resist developer composition, and then removing it, the photoresist pattern corresponding to the negative tone image can be completed.

[0071] Specific examples of the metal compounds contained in the aforementioned metal-containing resist composition are as described above.

[0072] The following explains in detail how to develop and form patterns, using diagrams as examples.

[0073] Figure 2 is a cross-sectional view showing the process sequence to illustrate the pattern formation method.

[0074] Referring to Figure 2(a), the exposed photoresist film is developed to form the photoresist pattern 130P.

[0075] 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.

[0076] 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.

[0077] Referring to Figure 2(b), the feature layer 110 is processed using the photoresist pattern 130P with the result of (a).

[0078] 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.

[0079] 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.

[0080] Another embodiment of the pattern formation method includes the steps of: applying a metal-containing resist composition onto a substrate; applying the aforementioned metal-containing resist edge bead removal composition along the edge of the substrate; a heat treatment step of drying and heating to form a metal-containing resist film on the substrate; exposing the metal-containing photoresist film; and developing it using the aforementioned metal-containing resist developer composition.

[0081] The specific methods for each stage are as described above. By simultaneously using the edge bead removal composition for metal-containing resists or the developing solution composition for metal-containing resists according to the present invention in the edge bead removal stage and the developing stage, the edge bead removal effect and the solubility of the unexposed areas are effectively improved, thereby satisfying the requirements for processing and patterning even smaller features and achieving excellent contrast characteristics, excellent sensitivity, and reduced line edge roughness (LER). [Examples]

[0082] The present invention will be described in more detail below through examples relating to the production of the aforementioned metal-containing resist edge bead removal composition and metal-containing resist developer composition. However, the technical features of the present invention are not limited by the following examples.

[0083] Composition for removing edge beads from metal-containing resists Example 1 After mixing the polyphenol compound and solvent according to the composition shown in Table 1 below, shake at room temperature (25°C) to completely dissolve them. Then, pass the mixture through a PTFE filter with a pore size of 1 μm to obtain the final composition.

[0084] Examples 2-7 and Comparative Examples 1-3 The composition is obtained in the same manner as in Example 1, except that the composition is changed to that shown in Table 1 below.

[0085] [Table 1]

[0086] A1: Tannic acid A2: Ellagic acid A3: Chrysophanol A4: Usnic acid A5: Formic acid A6: Acetic acid A7: 4-methylcatechol A8: Quercetin A9: Resveratrol PGMEA: Propylene glycol methyl ether acetate PGME: Propylene glycol methyl ether

[0087] Manufacturing of developer compositions for metal-containing resists Example 7 After mixing the polyphenol compound and solvent according to the composition shown in Table 2 below, shake at room temperature (25°C) to completely dissolve them. Then, pass the mixture through a PTFE filter with a pore size of 1 μm to obtain the final composition.

[0088] Examples 8-10 and Comparative Examples 4-6 The composition is obtained in the same manner as in Example 7, except that the composition is changed to that shown in Table 2 below.

[0089] [Table 2]

[0090] Manufacturing of organometallic photoresist compositions Manufacturing example An organometallic compound having the structural unit of the following chemical formula C (weight-average molecular weight: 1,500 g / mol) is 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.

[0091] [ka]

[0092] Evaluation 1: Evaluation of residual film thickness (Strip test) and evaluation of residual Sn before development. 1.0 mL of the organometallic compound-containing photoresist composition according to the above manufacturing example was placed on a 6-inch silicon wafer and allowed to stand for 20 seconds, then spin-coated at a speed of 800 rpm for 30 seconds. After that, the thickness of the coating film obtained by heat treatment at 180°C for 60 seconds was measured using the ellipsometry method. 10 mL each of the edge bead removal compositions obtained from Examples 1 to 7 and Comparative Examples 1 to 3 were placed along the edge of the wafer with the coated film, spin-coated for 5 seconds, and then dried by rotating at a speed of 1,500 rpm. After that, the thickness of the film obtained by heat treatment at 150°C for 60 seconds was remeasured using the ellipsometry method to confirm the change in thickness before and after the edge bead removal process and evaluated according to the following criteria. VPD ICP-MS analysis was performed to confirm the amount of residual Sn, and the results are shown in Table 3 below.

[0093] *If residual thickness is less than 2 Å: ○, if it is 2 Å or more: X

[0094] [Table 3]

[0095] Referring to Table 3, it can be confirmed that the metal-containing resist edge bead removal composition according to the example is superior to the metal-containing resist edge bead removal composition according to the comparative example in its metal removal effect and can further promote the reduction of residual metal.

[0096] Rating 2: Defective rating The aforementioned organometallic photoresist (PR) composition was spin-coated onto an 8-inch wafer at 1,500 rpm for 30 seconds, and then heat-treated at 160°C for 60 seconds to produce a coated wafer.

[0097] The developer compositions obtained from Examples 7 to 10 and Comparative Examples 7 to 14 were applied, and a development process was performed at a spin of 1,500 rpm for 30 seconds, followed by curing at 240°C for 60 seconds.

[0098] After the curing process was completed, wafer defects were measured using a surface inspection machine [SurfScan (SP2) manufactured by KLA Tencor]. Based on the number of defects with a size of 0.3 μm or less, a result of less than 150 defects was indicated as 'Good', and a result of 150 or more defects was indicated as 'Bad'.

[0099] Evaluation 3: ArF pattern evaluation The aforementioned organometallic photoresist (PR) composition 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.

[0100] This was exposed to an ArF immersion lithography system (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) in an L / S pattern at 20-35 mJ, then baked (PEB) at 100°C for 60 seconds. The developer compositions obtained from Examples 7-10 and Comparative Examples 7-14 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 from the generated patterns.

[0101] [Formula 1] Pattern collapse rate = {(Number of collapsed patterns) / (Total number of patterns)} * 100 (%) [Evaluation Criteria] ○: Pattern breakdown occurrence rate <60% X: Pattern collapse occurrence rate ≥ 60%

[0102] [Table 4]

[0103] Referring to Table 4, it can be seen 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.

[0104] Although specific embodiments of the present invention have been described and illustrated above, it is obvious to those ordinary skill in the art that the present invention is not limited to the described embodiments and can be modified and transformed in various ways without departing from the spirit and scope of the invention. Therefore, such modifications or variations should not be understood individually from the technical spirit or viewpoint of the present invention, and the modified embodiments should be considered to fall within the scope of the claims of the present invention. [Explanation of Symbols]

[0105] 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. Polyphenol compounds; and organic solvents, The aforementioned polyphenol compound is present in an amount of 10 to 50% by weight based on 100% by weight of the entire composition, wherein this is a composition for removing edge beads from metal-containing resists or a developer solution composition for metal-containing resists.

2. The composition for removing edge beads from metal-containing resists or the developer composition for metal-containing resists according to claim 1, wherein the polyphenol compound is contained in an amount of 10 to 30% by weight based on 100% by weight of the entire composition.

3. The composition for removing edge beads from metal-containing resists or the developer composition for metal-containing resists according to claim 1, wherein the polyphenol compound further comprises at least one carbonyl group.

4. The composition for removing edge beads from a metal-containing resist or a developer for a metal-containing resist according to claim 1, wherein the polyphenol compound is at least one selected from the group consisting of tannic acid, ellagic acid, chrysophanol, usnic acid, quercetin, and resveratrol.

5. The metal compound contained in the metal-containing resist 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 resist or a developer solution composition for a metal-containing resist.

6. The metal compound contained in the metal-containing resist is represented by the following chemical formula 1, and is the edge bead removal composition for the metal-containing resist or the developer composition for the metal-containing resist according to claim 5: 【Chemistry 1】 In the above chemical formula 1, R １ 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 ２ to R ４ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, alkoxy and aryloxy (—OR ａ , where R ａ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), a carboxyl group (—O(CO)R ｂ , R ｂ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), an alkylamide or dialkylamide (—NR ｃ R ｄ , where R ｃ and R ｄ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), an amidato (—NR ｅ (COR ｆ ), where R ｅ and R ｆ Each 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 ２ ~R ４ 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 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 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.)

7. The metal compound contained in the metal-containing resist is represented by the following chemical formula 2 or chemical formula 3, and is the edge bead removal composition for the metal-containing resist or the developer composition for the metal-containing resist according to claim 1: 【Chemistry 2】 In the above chemical formula 2, R ５ is a hydrocarbyl group having 1 to 31 carbon atoms, where 0 < z ≤ 2 and 0 < (z + x) ≤ 4; 【Transformation 3】 In the above chemical formula 3, R ６ 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.

8. The step of applying a metal-containing resist composition onto a substrate; A step of applying a metal-containing resist edge bead removal composition according to any one of claims 1 to 7 along the edge of the substrate; A heat treatment step in which a metal-containing photoresist film is formed on the substrate by drying and heating; The step of exposing the metal-containing photoresist film; and A pattern formation method that includes the development step.

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

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

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