Patent Grant
8895226
1. Field
Embodiments relate to a coating composition for deep ultraviolet (DUV) filtering, a method of forming a photoresist pattern using the same, and a method of fabricating a semiconductor device by using the method.
2. Description of the Related Art
Semiconductor devices have become increasingly more integrated and smaller in size, which has led to ongoing demand for methods of precisely forming fine patterns. In particular, methods of precisely forming fine patterns that are relatively simple to conduct and are low cost are desirable.
Embodiments are directed to a coating composition for DUV filtering, method of forming photoresist pattern using the same and method of fabricating semiconductor device by using the method.
At least one of the above and other features and advantages may be realized by providing a coating composition for deep ultraviolet (DUV) filtering during an extreme ultraviolet (EUV) exposure, which may include: 100 parts by weight of a solvent including a first solvent, the first solvent being an alcohol-based solvent, and about 0.05 parts by weight to about 5 parts by weight of a coating polymer having a degree of absorption of about 50%/μm or greater with respect to 193-nm wavelength incident light. The coating polymer may include a backbone having a repeating unit including benzene, naphthalene, or anthracene, a branch bonded to a backbone, the branch having a repeating unit including benzene, naphthalene, or anthracene, or a repeating unit including a carboxyl group.
The coating polymer may include the branch bonded to a backbone, wherein the branch further includes a C1-C5 alkylene group between the backbone and the benzene, naphthalene, or anthracene.
The coating polymer may be selected from the group of poly(hydroxystyrene), a copolymer of a hydroxystyrene derivative and hydroxystyrene, novolac resin, and a mixture thereof.
The coating polymer may be a copolymer of a hydroxystyrene derivative and hydroxystyrene, the copolymer being a block-copolymer or a random copolymer and being represented by Formula 1 below:
<Formula 1>
wherein m and n are integers equal to or greater than 1, where 0.4≦m/(m+n)<1; and R1 is a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 alkoxycarbonyloxy group, a C2-C6 acetal group, a C2-C6 acrylate group, trifluoromethyl, trichloromethyl, tribromomethyl, or a halogen atom.
The coating polymer may have a degree of absorption of about 40%/μm or greater with respect to 248-nm incident light. The coating polymer may have a degree of absorption of about 50%/μm or greater with respect to 220-nm incident light.
The first solvent may include a C2-C8 monohydric alcohol. The first solvent may include at least one selected from the group of methanol, ethanol, 1-propaneol, isopropaneol, n-propaneol, n-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, n-hexanol, cyclohexanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 2,2-dimethyl-3-pentanol, 2,3-dimethyl-3-pentanol, 2,4-dimethyl-3-pentanol, 4,4-dimethyl-2-pentanol, 3-ethyl-3-pentanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-methyl-2-hexanol, 2-methyl-3-hexanol, 5-methyl-1-hexanol, 5-methyl-2-hexanol, 2-ethyl-1-hexanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol, 1-octanol, 2-octanol, 3-octanol, 2-propyl-1-pentanol, 2,4,4-trimethyl-1-pentanol, 2,6-dimethyl-4-heptanol, 3-ethyl-2,2-dimethyl-pentanol, 1-nonanol, 2-nonanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, 2-decanol, 4-decanol, 3,7-dimethyl-1-octanol, and 3,7-dimethyl-3-octanol.
The solvent may include about 5 parts by weight to about 30 parts by weight of a second solvent, based on 100 parts by weight of the solvent, the second solvent including one selected from the group of ethyleneglycol, propyleneglycol, tetrahydrofuran, dioxane, ethyleneglycol monomethylether, ethyleneglycol monoethylether, ethyleneglycol dimethylether, ethyleneglycol diethylether, diethyleneglycol monomethylether, diethyleneglycol monoethylether, diethyleneglycol dimethylether, diethyleneglycol diethylether, diethyleneglycol ethylmethylether, propyleneglycol monomethylether, propyleneglycol monoethylether; ethyleneglycol ethyletheracetate, diethyleneglycol ethyletheracetate, propyleneglycol ethyletheracetate, propyleneglycol monomethyletheracetate; toluene, xylene, acetone, methylethylketone, methylisobutylketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, diacetonealcohol, acetic acidmethyl, acetic acidethyl, acetic acidpropyl, acetic acidbutyl, 2-hydroxypropionic acid ethyl, 2-hydroxy-2-methylpropionic acid methyl, 2-hydroxy-2-methylpropionic acid ethyl, ethoxyacetic acid ethyl, hydroxyacetic acid ethyl, 2-hydroxy-3-methylbutanoic acid methyl, 3-methoxypropionic acid methyl, 3-methoxypropionic acid ethyl, 3-ethoxypropionic acid ethyl, 3-ethoxypropionic acid methyl, water, and a mixture thereof.
The coating polymer may have a solubility with respect to the first solvent that is about 10 times greater than that of a (meth)acrylate-based resin with respect to the first solvent. The coating polymer may have a weight average molecular weight of about 2,000 to about 100,000, as measured by gel permeation chromatography (GPC). The coating composition may further include a photo-acid generator (PAG). The coating composition may further include a surfactant. The coating polymer may be included in an amount of about 0.1 parts by weight to about 3 parts by weight. The coating polymer may be included in an amount of about 0.3 parts by weight to about 2.5 parts by weight.
At least one of the above and other features and advantages may also be realized by providing a method of forming a photoresist pattern, the method including: forming a first layer of a photoresist composition for extreme ultraviolet (EUV) on a substrate, forming a second layer of a coating composition for deep ultraviolet (DUV) filtering on the first layer, exposing the first and second layers with an exposure mask, and developing the first and second layers, wherein the coating composition for DUV filtering includes: 100 parts by weight of a solvent including a first solvent, the first solvent being an alcohol-based solvent, and about 0.05 parts by weight to about 5 parts by weight of a coating polymer having a degree of absorption of about 50%/μm or greater with respect to 193-nm incident light.
The second layer may have a thickness of about 5 nm to about 100 nm. The coating polymer may include a backbone having a repeating unit including benzene, naphthalene, or anthracene, a branch bonded to a backbone, the branch having a repeating unit including benzene, naphthalene, or anthracene, or a repeating unit including a carboxyl group. The coating polymer may include the branch bonded to a backbone, the branch further including a C1-C5 alkylene group between the backbone and the benzene, naphthalene, or anthracene.
The coating polymer may be selected from the group of poly(hydroxystyrene), a copolymer of a hydroxystyrene derivative and hydroxystyrene, novolac resin, and a mixture thereof. The coating polymer may be a copolymer of a hydroxystyrene derivative and hydroxystyrene, the copolymer being a block-copolymer or a random copolymer and being represented by Formula 1 below:
wherein m and n are integers equal to or greater than 1, where 0.4≦m/(m+n)<1; and R1 is a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 alkoxycarbonyloxy group, a C2-C6 acetal group, a C2-C6 acrylate group, trifluoromethyl, trichloromethyl, tribromomethyl, or a halogen atom.
The first solvent may include a C2-C8 monohydric alcohol.
The method may further include post-exposure baking (PEB) between the exposing and the developing of the first and second layers, wherein the PEB is performed at a temperature of about 50° C. to about 200° C.
The photoresist composition for EUV may include a positive photoresist.
Developing of the first and second layers may include developing the first and second layers by using a developing solution, wherein the coating polymer is soluble in the developing solution. Developing the first and second layers may include almost completely removing the second layer by the developing solution. The developing solution may be an alkali solution.
The method may further include baking the first layer before the forming of the second layer. The method may further include baking the second layer before exposing of the first and second layers. The coating polymer may be included in an amount of about 0.1 parts by weight to about 3 parts by weight. The coating polymer may be included in an amount of about 0.3 parts by weight to about 2.5 parts by weight.
At least one of the above and other features and advantages may also be realized by providing a method of fabricating a semiconductor device including forming a photoresist pattern on a semiconductor substrate, and etching a layer underlying the photoresist pattern with the photoresist pattern as an etch mask, wherein forming the photoresist pattern on the semiconductor substrate includes: forming a first layer of a photoresist composition for extreme ultraviolet (EUV) on the semiconductor substrate, forming a second layer of a coating composition for deep ultraviolet (DUV) filtering on the first layer, the coating composition for DUV filtering including 100 parts by weight of a solvent having a first solvent that is an alcohol-based solvent, and about 0.05 parts by weight to about 5 parts by weight of a coating polymer having a degree of absorption of about 50%/μm or greater with respect to 193-nm incident light, exposing the first and second layers with an exposure mask, and developing the first and second layers.
The semiconductor substrate may include: a base substrate, and a first material layer on the base substrate, the first material layer having an etch selectivity with respect to the base substrate, and etching the layer includes etching the photoresist pattern, using the photoresist pattern as the etch mask.
At least one of the above and other features and advantages may also be realized by providing a semiconductor wafer, including: a semiconductor substrate, an extreme ultraviolet (EUV) photoresist layer on the semiconductor substrate, and a deep ultraviolet (DUV)-filtering coating layer on the EUV photoresist layer, wherein the DUV-filtering coating layer has a degree of absorption of about 50%/μm or greater with respect to incident light having a wavelength of about 193 nm.
At least one of the above and other features and advantages may also be realized by providing a method of forming a photoresist pattern, the method including: forming a first layer of a photoresist composition for extreme ultraviolet (EUV) on a substrate, forming a deep ultraviolet (DUV) shield layer on the first layer, exposing the first layer with an exposure mask, and developing the first layer.
The embodiments will become more apparent to those of ordinary skill in the art by describing in detail exemplary embodiments with reference to the attached drawings, in which:
Example embodiments will now be described more fully hereinafter with reference to the accompanying drawings; however, they may be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Like reference numerals refer to like elements throughout
In the drawing figures, the dimensions of layers and regions may be exaggerated for clarity of illustration. It will also be understood that when a layer or element is referred to as being “on” another layer or substrate, it can be directly on the other layer or substrate, or intervening layers may also be present. Further, it will be understood that when a layer is referred to as being “under” another layer, it can be directly under, and one or more intervening layers may also be present. In addition, it will also be understood that when a layer is referred to as being “between” two layers, it can be the only layer between the two layers, or one or more intervening layers may also be present. Like reference numerals refer to like elements throughout.
It will be understood that, although the terms first, second, third, etc., may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section, and vice versa, without departing from the teachings of the present invention.
The terms used herein are for the purpose of describing particular embodiments only and are not intended to be limiting of the invention. As used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising,” when used in this specification, specify the presence of stated features, integers, steps, operations, layers, regions, elements, components, and/or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, operations, layers, regions, elements, components, and/or groups thereof.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
In order to implement a half pitch resolution of less than 40 nm, lithography using an extremely short-wavelength light source, for example, an extreme ultraviolet (EUV) light source having a wavelength of about 13.5 nm, may be used. However, light emitted from a EUV light source may include both in-band light (intended for use in EUV lithography) and partially out-of-band light of 100-400 nm, (not intended for use). The out-of-band light may be a deep ultraviolet (DUV) wavelength of light and may be approximately 1-10% of the total light intensity.
Coating compositions for DUV filtering, according to embodiments, may partially or fully exclude such out-of-band light, and thus may improve resolution and variance of a pattern formed by EUV lithography.
In an implementation, the coating composition for DUV filtering may include a solvent and a coating polymer. The coating composition may include about 0.05 parts by weight to about 5 parts by weight of the coating polymer with respect to 100 parts by weight of the solvent. The solvent may include a first solvent that is an alcohol-based solvent. According to an embodiment, the amount of the coating polymer with respect to the solvent may be sufficient, e.g. not too small, to facilitate removal of the solvent in a relatively short time, and to avoid a coating layer of the coating polymer that is too thin. In addition, the amount of the coating polymer with respect to the solvent may be sufficient, e.g., not too large, to facilitate achieving a uniform thickness of a coated layer. The amount of the coating polymer may be from about 0.1 parts by weight to about 3 parts by weight, and in some embodiments, from about 0.3 parts by weight to about 2.5 parts by weight.
For example, the first solvent, which is an alcohol-based solvent, may include at least one of methanol, ethanol, 1-propaneol, isopropaneol, n-propaneol, n-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, n-hexanol, cyclohexanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 2,2-dimethyl-3-pentanol, 2,3-dimethyl-3-pentanol, 2,4-dimethyl-3-pentanol, 4,4-dimethyl-2-pentanol, 3-ethyl-3-pentanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-methyl-2-hexanol, 2-methyl-3-hexanol, 5-methyl-1-hexanol, 5-methyl-2-hexanol, 2-ethyl-1-hexanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol, 1-octanol, 2-octanol, 3-octanol, 2-propyl-1-pentanol, 2,4,4-trimethyl-1-pentanol, 2,6-dimethyl-4-heptanol, 3-ethyl-2,2-dimethyl-pentanol, 1-nonanol, 2-nonanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, 2-decanol, 4-decanol, 3,7-dimethyl-1-octanol, and 3,7-dimethyl-3-octanol. The first solvent may be a C2-C8 monohydric alcohol.
The coating polymer may be a polymer that is soluble in a solvent. For example, the coating polymer may include (i) a polymer including a backbone having a repeating unit including benzene, naphthalene, or anthracene, (ii) a polymer including a branch bonded to a backbone, the branch including a repeating unit including benzene, naphthalene, or anthracene, and/or (iii) a polymer having a repeating unit including a carboxyl group. The repeating unit of the branch may further include a C1-C5 alkylene group between the backbone and the benzene, naphthalene, or anthracene.
These repeating units may be from about 30 wt % to about 100 wt % of the respective polymers. For example, the repeating units may be from about 50 wt % to about 95 wt % of the respective polymers, and in some embodiments, from about 60 wt % to about 90 wt %.
The polymer including a backbone having a repeating unit of benzene may be a novolac resin.
The polymer having the branch including a repeating unit including benzene may be poly(hydroxystyrene) or a polymer of a hydroxystyrene derivative in which hydrogen of the hydroxyl group is substituted with methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, t-butoxycarbonyloxy, acetal, or t-butylacrylate.
The polymer including the branch having a repeating unit including naphthalene or anthracene may be a polymer including any of repeating units represented by Formulae 2-5 below, or a polymer analogous to these polymers.
The polymer having a repeating unit including a carboxyl group may be a polymer of vinyl-based monomers including carboxyl groups, such as polyacrylic acid, or polymethacrylic acid.
In some embodiments, the coating polymer may be at least one selected from the group of poly(hydroxystyrene), a copolymer of a hydroxystyrene derivative and hydroxystyrene, novolac resin, and a mixture thereof.
The coating polymer may be a copolymer of a hydroxystyrene derivative and hydroxystyrene that are block-copolymerized or randomly copolymerized to have a structure represented by Formula 1 below.
(wherein m and n are integers of 1 or greater, where 0.4≦m/(m+n)<1; and R1 is a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 alkoxycarbonyloxy group, a C2-C6 acetal group, a C2-C6 acrylate group, trifluoromethyl, trichloromethyl, tribromomethyl, or a halogen atom)
In some embodiments, R1 in Formula 1 may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, t-butoxycarbonyloxy, acetal, or t-butylacrylate.
Although the coating composition may have a random polymer structure, the coating composition, according to embodiments, may be represented by Formula 1 with an indication of the number of repeating units for convenience of illustration. The coating polymer of Formula 1 may include only one kind of hydroxystyrene derivative. However, in some embodiments the coating polymer may be a copolymer including two or more kinds of hydroxystyrene derivatives. The percentage of hydroxystyrene repeating units may be about 40% or greater in number, irrespective of the kinds of hydroxystyrene derivatives in the copolymer.
The coating polymer may have a degree of absorption of about 50%/μm or greater, with respect to incident light having a wavelength of 193 nm. In some embodiments, the coating polymer may have a degree of absorption of about 60%/μm or greater with respect to incident light having a wavelength of 193 nm. In some embodiments, the coating polymer may have a degree of absorption of about 65%/μm or greater with respect to incident light having a wavelength of 193 nm.
In some embodiments, the coating polymer may have a degree of absorption of about 50%/μm or greater with respect to incident light having a wavelength of 220 nm. In some embodiments, the coating polymer may have a degree of absorption of about 60%/μm or greater with respect to incident light having a wavelength of 220 nm. In some embodiments, the coating polymer may have a degree of absorption of about 65%/μm or greater with respect to incident light having a wavelength of 220 nm.
In some embodiments, the coating polymer may have a degree of absorption of about 40%/μm or greater with respect to incident light having a wavelength of 248 nm. In some embodiments, the coating polymer may have a degree of absorption of about 45%/μm or greater with respect to incident light having a wavelength of 248 nm. In some embodiments, the coating polymer may have a degree of absorption of about 50%/μm or greater with respect to incident light having a wavelength of 248 nm.
The term “degree of absorption” as used herein, refers to a percentage of light absorbed by a layer, rather than transmitted through the layer, per unit thickness of the layer with respect to the amount of light incident on the layer.
The degree of absorption may be quantitated in terms of transmittance. The term “transmittance,” as used herein, refers to a percentage of light passing through a layer per unit thickness of the layer with respect to the amount of light incident on the layer. The degree of absorption of the coating polymer may be determined from transmittance. For example, the coating polymer may have a transmittance of about 50%/μm or less with respect to incident light having a wavelength of 193 nm. In some embodiments, the coating polymer may have a transmittance of about 40%/μm or less with respect to incident light having a wavelength of 193 nm. In some embodiments, the coating polymer may have a transmittance of about 35%/μm or less with respect to incident light having a wavelength of 193 nm.
In some embodiments, the coating polymer may have a transmittance of about 50%/μm or less with respect to incident light having a wavelength of 248 nm. In some embodiments, the coating polymer may have a transmittance of about 45%/μm or less with respect to incident light having a wavelength of 248 nm. In some embodiments, the coating polymer may have a transmittance of about 40%/μm or less with respect to incident light having a wavelength of 248 nm.
The coating polymer may have a weight average molecular weight of about 2,000 to about 100,000, as measured by gel permeation chromatography (GPC). The weight average molecular weight of the coating polymer may be sufficient, e.g., not too small, to facilitate achieving a composition of the coating polymer with a high enough viscosity to form a film. In addition, the weight average molecular weight of the coating polymer may be sufficient, e.g., not too large, to facilitate controlling the thickness of a film.
A compound, including a cyclic hydrocarbon such as benzene, naphthalene, or anthracene in a backbone or branch, may more efficiently absorb a DUV wavelength of light of less than 200 nm than a DUV wavelength of light of 200 nm or greater. It may be inferred from this that a coating composition for DUV filtering may have a higher degree of absorption with respect to 194-nm DUV light than to 220-nm or 249-nm DUV light.
The coating polymer may have a polydispersity index (PDI) of about 1.0 to about 2. The PDI of the coating polymer may be sufficient, e.g., not too high, to facilitate controlling physical characteristics of a film formed from the coating polymer.
The first solvent may be chosen to ensure that the coating polymer has a high solubility. The first solvent may be chosen to ensure that the coating polymer has a solubility that is about 10 times higher than that of (meth)acrylate-based resin with respect to the first solvent. The (meth)acrylate-based resin may be an aliphatic (meth)acrylate-based polymer. Examples of the (meth)acrylate-based polymer may include one selected from the group of polymethylmethacrylate (PMMA), poly(t-butylmethacrylate), poly(methacrylic acid), poly(norbornylmethacrylate), binary or higher multiple copolymers thereof, and mixtures thereof. However, other (meth)acrylate-based polymer may be included in the binary or higher multiple copolymers.
In order to facilitate control of coating characteristics, the coating composition for DUV filtering may include about 5 parts by weight to about 30 parts by weight of a second solvent with respect to 100 parts by weight of the entire solvent. Coating characteristics of the coating composition for DUV filtering may be dependant on the viscosity thereof, surface characteristics of a target to be coated, and the like. By adding the second solvent to the first solvent, the viscosity of the coating composition and the surface characteristics of the target may be controlled, thereby facilitating control or adjustment of the coating characteristics. The amount of the second solvent may be sufficient, e.g., not too large, to prevent erosion of a photoresist film contacting the second solvent, and/or inter-mixing of the photoresist film with the second solvent.
Examples of the second solvent may include ethyleneglycol, propyleneglycol, tetrahydrofuran, dioxane, ethyleneglycol monomethylether, ethyleneglycol monoethylether, ethyleneglycol dimethylether, ethyleneglycol diethylether, diethyleneglycol monomethylether, diethyleneglycol monoethylether, diethyleneglycol dimethylether, diethyleneglycol diethylether, diethyleneglycol ethylmethylether, propyleneglycol monomethylether, propyleneglycol monoethylether; ethyleneglycol ethyletheracetate, diethyleneglycol ethyletheracetate, propyleneglycol ethyletheracetate, propyleneglycol monomethyletheracetate; toluene, xylene, acetone, methylethylketone, methylisobutylketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, diacetonealcohol, acetic acidmethyl, acetic acidethyl, acetic acidpropyl, acetic acidbutyl, 2-hydroxypropionic acid ethyl, 2-hydroxy-2-methylpropionic acid methyl, 2-hydroxy-2-methylpropionic acid ethyl, ethoxyacetic acid ethyl, hydroxyacetic acid ethyl, 2-hydroxy-3-methylbutanoic acid methyl, 3-methoxypropionic acid methyl, 3-methoxypropionic acid ethyl, 3-ethoxypropionic acid ethyl, 3-ethoxypropionic acid methyl, water, and a mixture thereof.
The coating composition for DUV filtering may further include an acid generator. For example, the acid generator may be a photo-acid generator (PAG). Any suitable acid generators that are known in the art may be used. Examples of suitable acid generators may include onium salts, halogen compounds, nitrobenzyl esters, alkylsulfonates, diazonaphtoquinones, iminosulfonates, disulfones, diazomethanes, and sulfonyloxyketones. In the coating composition for DUV filtering, the amount of the acid generator may be from about 1 wt % to about 20 wt %, based on the weight of the coating polymer.
If desired, the coating composition for DUV filtering may further include a surfactant. In order to have improved coating characteristics. Any suitable surfactants that are known in the art may be used. For example, at least one selected from among cationic surfactants, anionic surfactants, non-ionic surfactants, and amphoteric surfactants may be used. Examples of suitable surfactants include fluorine-based surfactants commercially available under various product names, including BM-1000, BM-1100 (available from BM Chemie Co.); MEGAFAC F142D, MEGAFAC F172, MEGAFAC F173, MEGAFAC F183 (available from Dainippon Ink & Chemicals, Inc.); FLUORAD FC-135, FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431 (available from Suminoto 3M); SURFLON S-112, SURFLON S-113, SURFLON S-131, SURFLON S-141, SURFLON S-145 (available from Asahi Glass Co., Ltd); SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (available from Toray Dow Corning Silicone Co., Ltd); and NBX-15 (available from NEOS Co.), and non-fluorine-based surfactants commercially available under various product names, including POLYFLOW No. 75 (Kyoeisha Chemical Co., Ltd.). The amount of the surfactant may be from about 0.5 wt % to about 5 wt % of the weight of the coating composition.
The coating composition for DUV filtering may be useful for blocking out-of-band light of about 100 nm to about 400 nm, not intended for use in EUV lithography, and in some embodiments, out-of-band of light of about 100 nm to about 300 nm.
Hereinafter, methods of forming photoresist patterns on a substrate by using the coating composition for DUV filtering, according to embodiments of the inventive concept will be described. According to an embodiment, there is provided a method of forming a photoresist pattern on a substrate by using the coating composition for DUV filtering. The substrate may be a silicon substrate, a silicon-on-insulator (SOI) substrate, a silicon-germanium substrate, or a gallium-arsenide substrate. However, the substrate is not limited thereto and a variety of substrates may be used. For example, a bare wafer, or a substrate having a structure on an active surface thereof may be used.
According to the current embodiment, the method of forming a photoresist pattern may include: forming a first layer of a photoresist composition for EUV on the substrate; baking the first layer; forming a second layer of a coating composition for DUV filtering on the first layer; baking the second layer; exposing the first and second layers with an exposure mask; and developing the first and second layers. The coating composition for DUV filtering may include 100 parts by weight of a solvent (including a first solvent that is an alcohol-based solvent), and about 0.5 parts by weight to about 5 parts by weight of a coating polymer (having a degree of absorption of about 50%/μm or greater with respect to 193-nm incident light).
Hereinafter, the steps of the method, according to embodiments, will be described in more detail.
Referring to
The photoresist composition for EUV may include a photoresist composition, including a photoresist compound that may undergo chemical changes by EUV irradiation to have different solubilities in a developing solution. The photoresist compound may be a (meth)acrylate-based polymer. The (meth)acrylate-based polymer may be an aliphatic (meth)acrylate-based polymer. Examples of the (meth)acrylate-based polymer may include one of polymethylmethacrylate (PMMA), poly(t-butylmethacrylate), poly(methacrylic acid), poly(norbornylmethacrylate), (meth)acrylate-based polymers, binary or multiple copolymers thereof, and mixtures thereof. However, any suitable EUV photoresist polymer that is known in the art may be used as the photoresist compound. It will be understood by those of ordinary skill in the art that suitable EUV photoresist compositions are commercially available.
Suitable photoresist compounds may include positive photoresists and negative photoresists. In some embodiments, the photoresist compound may be a positive photoresist. In this regard, the positive photoresist may be easily removed using an alkali developing solution in a developing process.
The photoresist composition for EUV may further include an acid generator. In some embodiments, the acid generator may be a photo-acid generator (PAG). Any suitable acid generator that is known in the art may be used. Examples of suitable acid generators may include onium salts, halogen compounds, nitrobenzyl esters, alkylsulfonates, diazonaphtoquinones, iminosulfonates, disulfones, diazomethanes, and sulfonyloxyketones. In the photoresist composition for EUV, the amount of the acid generator may be from about 1 wt % to about 20 wt %, based on the weight of the photoresist compound.
The first layer 110 may be formed on the substrate 190 by using, in some embodiments, spin coating or roll coating. In some embodiments, before the forming of the first layer 110, a surface of the substrate 190 on which the first layer 110 is to be formed may be treated with a primer material, such as hexamethyldisilazane (HMDS) or trimethylsilyldiethylamine (TMSDEA), to enhance adhesion of the first layer 110 to the substrate 190.
Then, the first layer 110 may be soft-baked. The soft baking may be performed at a temperature of about 50° C. to about 150° C. for about 20 seconds to about 5 minutes. The soft baking may fully or partially remove a solvent from the first layer 110. However, the soft baking may be omitted depending on the viscosity and thickness of the first layer 110, and the kind of solvent used in the photoresist composition.
Referring to
A solvent for the coating composition for DUV filtering that may be used to form the second layer 120 may be a solvent that is barely able to dissolve the first layer 110. In an implementation, the solvent for the coating composition for DUV filtering may dissolve the coating polymer for DUV filtering well, and barely dissolves the photoresist compound of the first layer 110. For example, the coating composition for DUV filtering may dissolve the photoresist compound of the first layer 110 to a significantly lesser degree than the coating polymer for DUV filtering.
Then, the second layer 120 may be soft-baked. The soft baking may be performed at a temperature of about 50° C. to about 150° C. for about 20 seconds to about 5 minutes. The soft baking may fully or partially remove the solvent from the second layer 120. However, the soft baking may be omitted depending on the viscosity and thickness of the second layer 120, and the kind of the solvent used in the coating composition (i.e., miscibility with the solvent used to form the first layer 110).
The second layer 120 may have a thickness of about 5 nm to about 100 nm after the soft baking is complete. If the thickness of the second layer 120 is too small, the second layer 120 may not sufficiently absorb out-of-band light of the DUV wavelength. If the thickness of the second layer 120 is too large, the second layer 120 may insufficiently transmit in-band light of the EUV wavelength to expose the first layer 110 underlying the second layer 120
However, the exposure light emitted from a light source (not shown) may include, to some extent, a DUV wavelength of light, in some embodiments, of from about 100 nm to about 300 nm, as illustrated in
Referring to
Referring to
Next, post-exposure baking (PEB) may be performed at a temperature of about 50° C. to about 200° C. The PEB may be performed for about 20 seconds to about 150 seconds.
Referring to
The developing solution may be an alkali solution in which is dissolved, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silitate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammoniumhydroxide, tetraethylammoniumhydroxide, tetrapropylammoniumhydroxide, tetrabutylammoniumhydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, or 1,5-diazabicyclo-[4.3.0]-5-nonane. These developing solutions may further include an appropriate amount of an aqueous organic solvent selected from among alcohols including, for example, methanol or ethanol, or an appropriate amount of a surfactant. When such an alkali developing solution is used, the developing process may be followed by rinsing with deionized (DI) water or a mixture of DI water and a surfactant.
The developing solution may mainly serve to remove the exposed region 110b of the first layer 110. However, the exposed and unexposed regions 120a and 120b of the second layer 120 may be substantially completely removed by the developing solution.
The developing process may result in a photoresist pattern 140, as illustrated in
According to the embodiments, a method of fabricating semiconductor devices may include: forming a photoresist pattern on a semiconductor substrate; and etching a layer underlying the photoresist pattern with the photoresist pattern as an etch mask. The forming of the photoresist pattern on the semiconductor substrate may include: forming a first layer of a photoresist composition for EUV on a semiconductor substrate; forming a second layer of a coating composition for DUV filtering on the first layer; exposing the first and second layers with an exposure mask; and developing the first and second layers. In this regard, the coating composition for DUV filtering may include about 100 parts by weight of a solvent (including a first solvent that is an alcohol-based solvent); and about 0.05 parts by weight to about 5 parts by weight of a coating polymer (having a degree of absorption of about 50%/μm or greater with respect to 193-nm incident light). The amount of the coating polymer may be from about 0.1 parts by weight to about 3 parts by weight, and in some embodiments, from about 0.3 parts by weight to about 2.5 parts by weight.
Hereinafter, an embodiment of a method of fabricating a semiconductor device will be described with reference to
Referring to
The first material layer 294 may be a material layer having an etching selectivity with respect to the base substrate 292. Any suitable material layer may be used. In some embodiments, the first material layer 294 may be a silicon oxide layer, a silicon nitride layer, a silicon oxynitride layer, a metal layer, such as a copper, tungsten, or aluminum layer, a metal oxide layer, a metal nitride layer, a metal oxynitride layer, or the like.
Although
Referring to
Next, the first layer 210 and the second layer 220 may be exposed to an EUV wavelength of light through an exposure mask 230. Like the previously described embodiment, an exposure light source that emits the EUV wavelength of light may also emit a DUV wavelength of light to some extent. The DUV wavelength of light may be absorbed by the second layer 220, and thereby, be blocked from reaching the first layer 210, as seen in
Referring to
Next, referring to
Next, referring to
The structure 294a may be any of various types of structures. In some embodiments, the structure 294a may be a structure to define an active region, a line-and-space structure, an insulating layer structure including a hole(s), or the like. Those skilled in the art may understand methods of fabricating semiconductor devices by using these structures, and thus, a detailed description thereof will not be provided here.
Embodiments will be described in further detail with reference to the following experiments. These experiments are for illustrative purposes only and are not intended to limit the scope of the present inventive concept.
Coating compositions for DUV filtering including different concentrations of either Novolac resin (having a number-averaged molecular weight (Mn) of 6,724 and a polydispersity index (PDI) of 1.71) or polyhydroxystyrene (PHS) resin (having a Mn of 2988 and a PDI of 1.72) and different solvents, were used to test film forming characteristics (Experiments 1-34). Mixtures of the resins and solvents were stirred for 3 hours and were then filtered by using a 20-nm filter. Mn, Mw, and PDI were measured using a gel permeation chromatograph (GPC) (Waters, HPLC 2414). The column used was Shodex KF-803, and tetrahydrofuran (THF) was used as an eluent. In addition, polystyrene standard was used.
The filtrates were coated on 300-mm wafers at about 1,000 rpm by using a CLEAN TRACK ACT12 (Tokyo Electron Ltd.) and then were baked at about 120° C. or 60 seconds. Thicknesses of the resulting films were measured. The results are shown in Table 1 below.
Coating compositions for DUV filtering containing the same kinds of resins as used in Experiments 1-34, and each composition containing two kinds of solvents (first and second solvents), were used to test film forming characteristics, in the same manner as described above (Experiments 35-67). The results are shown in Table 2 below. The first solvent and the second solvent in each composition were mixed at a volume ratio of 9:1.
Referring to Tables 1 and 2, the coating compositions for DUV filtering according to Experiments 1-67 were found to form films having appropriate thicknesses.
Film Removal Test
Some of the films formed from the coating compositions of Experiments 1-67 were tested to determine if they could be removed by different developing solutions. The films were subjected to puddle development in a CLEAN TRACK ACT12 (available from Tokyo Electron Ltd.) for 60 seconds. Residual thicknesses of the films were measured to determine if there was any residue left after the development. The results are shown in Table 3 below.
Referring to Table 3, the films of Experiments 1-67 were found to be easily removable by these alkali developing solutions.
Miscibility Test Between Photoresist Film and DUV-Filtering Coating Film
Photoresists for EUV were spin-coated on 12-inch silicon wafers that were treated with hexamethyldisilazane (HMDS) at about 120° C. for about 60 seconds, at about 1,000 rpm, and were then soft-baked on a hot plate at about 110° C. for about 60 seconds to form photoresist films. Then, initial thicknesses of the photoresist films were measured.
After the original thickness measurements on the photoresist layers, the coating compositions for DUV filtering prepared above were spin-coated on the photoresist layers at about 1000 rpm, and were then soft-baked at about 90° C. for about 60 seconds to form DUV-filtering coating films. Then, thicknesses of the DUV-filtering coating films were measured.
Finally, the resulting structures were subjected to puddle development in a CLEAN TRACK ACT12 (available from Tokyo Electron Ltd.) for about 60 seconds, and residual thicknesses of the photoresist films were measured. The results are shown in Table 4 below.
Referring to Table 4, the structures of Experiments 88-95 exhibited nearly no difference between the initial and residual thicknesses of the photoresist films. This result indicates that the solvents in the coating compositions for DUV filtering were barely mixed with the photoresist films underlying the DUV-filtering coating films, or did not cause the photoresists to diffuse out.
DUV Absorption Test on DUV-Filtering Coating Film
Novolac resin (SAMPLE 1), PHS resin (SAMPLE 2), and a PHS/poly(t-BOC oxystyrene) random copolymer (SAMPLE 3) represented by Formula 6 were coated on transparent substrates respectively to form DUV-filtering coating films. The definitions of m and n in Formula 6 are as provided above. Then, degrees of absorption of the DUV-filtering coating films were measured at a wavelength range of about 200 nm to about 400 nm. The results are shown in
Referring to
Patterning Test
Photoresists for EUV were spin-coated on 12-inch silicon wafers that were treated with HMDS at about 120° C. for 60 seconds, at about 1,000 rpm and were then soft-baked at about 120° C. for about 60 seconds to form photoresist films each having a thickness of about 60 nm. Three samples for each different photoresist for EUV were prepared for comparison. Two types of coating compositions for DUV filtering were spin-coated on the photoresist films of two of the three samples for each different photoresist and were then soft-baked at about 90° C. for about 60 seconds to form DUV-filtering coating films. The remaining one sample was not coated with the coating composition for comparison.
The resulting structures on the silicon wafers were subjected to EUV exposures on an ASML ADT at a NA of 0.25 using conventional illumination, wherein an EUV mask having a 30-nm line-and-space pattern was used. The exposure process was followed by PEB at about 90° C. for about 60 seconds, and then, puddle development in a CLEAN TRACK ACT12 (available from Tokyo Electron Ltd.) for about 60 seconds. A 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution was used as a developing solution.
After the development was complete, the resulting patterns were observed using a Hitachi S-9220 to measure line width roughnesses (LWRs) of the patterns. The results are shown in Table 5.
Referring to Table 5, those samples coated with the coating compositions for DUV filtering (Experiments 96-103) were found to have more precise 30-nm line-and-space patterns, as compared to those samples coated only with the photoresists for EUV (Experiments 104-107), indicating that using the coating compositions for DUV filtering according to the embodiments may ensure more precise pattern formation.
Embodiments may relate to a coating composition for DUV filtering that facilitates precise formation of a fine pattern, a method of forming a photoresist pattern by using the coating composition, and a method of fabricating a semiconductor device by using the coating composition or the method.
Example embodiments have been disclosed herein, and although specific terms are employed, they are used and are to be interpreted in a generic and descriptive sense only and not for purpose of limitation. In some instances, as would be apparent to one of ordinary skill in the art as of the filing of the present application, features, characteristics, and/or elements described in connection with a particular embodiment may be used singly or in combination with features, characteristics, and/or elements described in connection with other embodiments unless otherwise specifically indicated. Accordingly, it will be understood by those of skill in the art that various changes in form and details may be made without departing from the spirit and scope of the present invention as set forth in the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2010-0071605 | Jul 2010 | KR | national |
This application is a Divisional of U.S. application Ser. No. 13/188,670, filed Jul. 22, 2011, issued on May 16, 2014 as U.S. Pat. No. 8,715,911, and which claims priority to Korean Patent Application No. 10-2010-0071605, filed on Jul. 23, 2010, in the Korean Intellectual Property Office, and entitled: “Coating Composition for DUV Filtering, Method of Forming Photoresist Pattern Using the Same and Method of Fabricating Semiconductor Device by Using the Method,” the disclosure of which is incorporated by reference herein in its entirety.
| Number | Name | Date | Kind |
|---|---|---|---|
| 20050008864 | Schenau et al. | Jan 2005 | A1 |
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| Number | Date | Country | |
|---|---|---|---|
| 20140205950 A1 | Jul 2014 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13188670 | Jul 2011 | US |
| Child | 14223540 | US |
