Pattern forming method and photoresist film

Abstract

The invention discloses a method for forming a pattern and a photoresist film. The method for forming the pattern comprises the following steps: coating a semiconductor photoresist composition containing an organic tin compound on a substrate; drying and heating to form a photoresist film; the organic tin compound has at least one organic ligand containing a Sn-C bond and at least one organic carbonyloxy group, and the photoresist film contains a compound represented by (R1Sn) xOy (OAR2) z before or after exposure, and the photoresist film contains a compound represented by (R1Sn) xOy (OAR2) z.

Description

[0001] Cross - reference to related applications

[0002] This application claims the priority and benefit of Korean Patent Application No. 10 - 2024 - 0001648, filed with the Korean Intellectual Property Office on January 4, 2024, the entire content of which is incorporated herein by reference. Technical field

[0003] Embodiments of the present disclosure relate to a method of forming a pattern and a photoresist film for forming a pattern. Background art

[0004] Extreme ultraviolet (EUV) lithography has attracted attention as an important technology for manufacturing next - generation semiconductor devices. EUV lithography is a pattern - forming technology that uses EUV rays with a wavelength of about 13.5 nanometers as an exposure light source. According to EUV lithography, extremely fine patterns (e.g., less than or equal to about 20 nanometers) can be formed in the exposure process during semiconductor device manufacturing.

[0005] EUV lithography is achieved by developing compatible photoresists that can be executed under conditions of a spatial resolution less than or equal to about 16 nanometers. Currently, efforts are being made to meet the specifications of traditional chemically amplified (CA) photoresists that are unsuitable or insufficient for next - generation devices in terms of resolution, photospeed, and feature roughness (also referred to as line edge roughness or LER).

[0006] The inherent image blur caused by acid - catalyzed reactions in these polymer - type photoresists limits the resolution of small feature sizes, which has long existed in electron beam (e - beam) lithography. Chemically amplified (CA) photoresists are designed for high sensitivity, but due to their general elemental composition, which reduces the light absorption rate of the photoresist at a wavelength of about 13.5 nanometers, thereby reducing their sensitivity, CA photoresists may face at least some more difficulties under EUV exposure.

[0007] CA photoresists may have difficulties in small feature sizes due to roughness problems, and experiments have shown that due to the nature of the acid - catalyzed process, as the photospeed decreases, the line edge roughness (LER) of CA photoresists increases at least in part. Therefore, due to these defects and problems of existing CA photoresists, high - performance photoresists would be beneficial to the semiconductor industry.

[0008] To overcome the disadvantages of the above-described chemically amplified (CA) organic photosensitive compositions, inorganic photosensitive compositions have been studied. Inorganic photosensitive compositions are mainly used for negative-tone patterning with resist composition removability by chemical modification through a non-chemical amplification mechanism. Such inorganic photosensitive compositions contain inorganic elements with higher EUV absorption rates than related hydrocarbons, and thus can ensure sensitivity through a non-chemical amplification mechanism and are less sensitive to random effects, and thus have low line-edge roughness and fewer defects.

[0009] Inorganic photoresists based on tungsten peroxypolyacids mixed with tungsten, niobium, titanium, and / or tantalum have been reported as radiation-sensitive materials for patterning.

[0010] The above materials are effective for large-pitch patterning in a bilayer configuration for far-ultraviolet (deep-ultraviolet), X-ray, and electron beam light sources. Recently, impressive performance has been obtained when imaging a 15-nanometer half-pitch (HP) by projection EUV exposure using a cationic hafnium metal oxide sulfate (HfSOx) material together with a peroxo complexing agent. The above system exhibits the highest performance of non-CA photoresists and has a practical photosensitivity speed close to an appropriate level for EUV photoresists. However, the hafnium metal oxide sulfate materials with peroxo complexing agents have some practical disadvantages. First, these materials are coated in a corrosive sulfuric acid / hydrogen peroxide mixture and have inappropriate or insufficient shelf-life stability. Second, structural changes for performance improvement as a composite mixture are not easy. Third, development should be carried out in a solution of approximately 25 wt% tetramethylammonium hydroxide (TMAH) and / or the like with extremely high concentration.

[0011] Recently, active research has been conducted on tin-containing molecules that have excellent absorption of extreme ultraviolet light. Among them, for organotin polymers, alkyl ligands are dissociated by light absorption or the resulting secondary electrons and crosslinked with adjacent chains through oxygen bonds, thereby achieving negative-tone patterning that cannot be removed by an organic developer. The above organotin polymers exhibit greatly improved sensitivity while maintaining resolution and line-edge roughness, but for commercial availability, the patterning characteristics need to be further improved. SUMMARY OF THE INVENTION

[0012] A method of forming a pattern according to some embodiments provides a pattern with improved sensitivity.

[0013] Some embodiments relate to a photoresist film provided in a method of forming a pattern.

[0014] A method of forming a pattern according to some embodiments includes coating a semiconductor photoresist composition comprising an organotin compound on a substrate; drying and heating to form a photoresist film; and exposing and developing the photoresist film, wherein the organotin compound has at least one organic ligand including an Sn-C bond and at least one organic carbonyloxy group, and the photoresist film includes, before or after exposure, a compound represented by (R 1 Sn) x O y (OAR 2 ) z (wherein x, y, and z are each independently from 0.1 to 0.9, x + y + z = 1, A is a single bond (e.g., a single covalent bond) or C=O, R 1 is selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aralkyl, and L a -O-R a (wherein L a is a substituted or unsubstituted C1-C20 alkylene, and R a is a substituted or unsubstituted C1-C20 alkyl), and R 2 is hydrogen, a substituted or unsubstituted C1-C20 alkyl, a substituted or unsubstituted C3-C20 cycloalkyl, a substituted or unsubstituted C2-C20 alkenyl, a substituted or unsubstituted C2-C20 alkynyl, a substituted or unsubstituted C6-C30 aryl, or a combination thereof).

[0015] A photoresist film according to some embodiments includes a compound represented by (R 1 Sn) x O y (OAR 2 ) z .

[0016] By using the method of forming a pattern according to some embodiments, sensitivity can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The drawings, together with the specification, illustrate embodiments of the subject matter of the present disclosure and, together with the description, are used to explain the principles of the embodiments of the present disclosure.

[0018] Figures 1 - 5 is a cross-sectional view for explaining a method of forming a pattern using a semiconductor photoresist composition according to some embodiments.

[0019] REFERENCE NUMERAL DESCRIPTION

[0020] 100: Semiconductor substrate / substrate

[0021] 102: Thin film

[0022] 104: Resist underlayer

[0023] 106: Photoresist film

[0024] 106a: Exposed area

[0025] 106b: Unexposed area

[0026] 108: Photoresist pattern

[0027] 110: Patterned mask

[0028] 112: Organic film pattern

[0029] 114: Thin film pattern Detailed implementation mode

[0030] Hereinafter, embodiments of the present disclosure will be described in more detail with reference to the accompanying drawings. In the following description of the present disclosure, well-known functions or structures will not be described in order to clarify the subject matter of the present disclosure.

[0031] In order to clearly illustrate the embodiments of the present disclosure, certain descriptions and relationships may be omitted, and throughout the disclosure, the same or similar configuration elements are designated by the same reference numerals. In addition, since the dimensions and thicknesses of each configuration shown in the drawings may be arbitrarily shown for better understanding and convenience of description, the present disclosure is not necessarily limited thereto.

[0032] In the drawings, the thicknesses of layers, films, panels, regions, etc. may be exaggerated for clarity. In the drawings, the thicknesses of some layers or regions, etc. may be exaggerated for clarity. It should be understood that if an element such as a layer, film, region, or substrate is referred to as being "on" another element, it may be directly on the other element, or there may also be intervening elements.

[0033] As used herein, "substituted" means that a hydrogen atom is replaced by deuterium, a halogen, a hydroxyl group, a mercapto group, a cyano group, a nitro group, -NRR' (wherein R and R' are each independently hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated cycloaliphatic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), -SiRR'R" (wherein R, R' and R" are each independently hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated cycloaliphatic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), a C1 to C30 alkyl group, a C1 to C10 haloalkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a C1 to C20 thioether group, or a combination thereof. "Unsubstituted" means that the hydrogen atom is not replaced by another substituent and retains the hydrogen atom.

[0034] As used herein, if no other definition is provided, "alkyl" means a linear or branched aliphatic hydrocarbon group. The alkyl group can be a "saturated alkyl" group that does not contain any double or triple bonds.

[0035] The alkyl group can be a C1 to C8 alkyl group. For example, the alkyl group can be a C1 to C7 alkyl group, a C1 to C6 alkyl group, or a C1 to C5 alkyl group. For example, a C1 to C5 alkyl group can be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or 2,2-dimethylpropyl.

[0036] As used herein, if no other definition is provided, "cycloalkyl" means a monovalent cyclic aliphatic hydrocarbon group.

[0037] The cycloalkyl group can be a C3 to C8 cycloalkyl group, for example, a C3 to C7 cycloalkyl group, a C3 to C6 cycloalkyl group, a C3 to C5 cycloalkyl group, or a C3 to C4 cycloalkyl group. For example, the cycloalkyl group can be cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, but is not limited thereto.

[0038] As used herein, "aliphatic unsaturated organic group" means a hydrocarbon group containing a bond (e.g., a covalent bond) wherein the bond between carbon atoms in the molecule is a double bond, a triple bond or a combination thereof.

[0039] The aliphatic unsaturated organic group may be a C2-C8 aliphatic unsaturated organic group. For example, the aliphatic unsaturated organic group may be a C2-C7 aliphatic unsaturated organic group, a C2-C6 aliphatic unsaturated organic group, a C2-C5 aliphatic unsaturated organic group, or a C2-C4 aliphatic unsaturated organic group. For example, the C2-C4 aliphatic unsaturated organic group may be vinyl, ethynyl, allyl, 1-propenyl, 1-methyl-1-propenyl, 2-propenyl, 2-methyl-2-propenyl, 1-propynyl, 1-methyl-1-propynyl, 2-propynyl, 2-methyl-2-propynyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-butynyl, 2-butynyl or 3-butynyl.

[0040] As used herein, "aryl" refers to a substituent in which all atoms in the cyclic substituent have p orbitals and these p orbitals are conjugated, and may include monocyclic or fused-ring polycyclic functional groups (e.g., rings sharing adjacent carbon atom pairs) functional groups.

[0041] As used herein, "heteroaryl" refers to an aryl containing at least one heteroatom selected from N, O, S, P, and Si. Two or more heteroaryls may be directly linked by a σ bond, or if the heteroaryl contains two or more rings, these two or more rings may be fused together. If the heteroaryl is a fused ring, each ring may contain one to three heteroatoms.

[0042] As used herein, unless otherwise defined, "alkenyl" refers to an aliphatic unsaturated alkenyl of a straight-chain or branched-chain aliphatic hydrocarbon group containing at least one double bond.

[0043] As used herein, unless otherwise defined, "alkynyl" refers to an aliphatic unsaturated alkynyl of a straight-chain or branched-chain aliphatic hydrocarbon group containing at least one triple bond.

[0044] The organotin compound may include at least one group selected from organic oxy and organic carbonyloxy groups.

[0045] The organotin compound may be represented by Chemical Formula 1.

[0046] Chemical Formula 1

[0047]

[0048] In Chemical Formula 1,

[0049] R 3 Selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aralkyl, and L a-O-R a (wherein L a is a substituted or unsubstituted C1-C20 alkylene group, and R a is a substituted or unsubstituted C1-C20 alkyl group), selected from

[0050] R 4 to R 6 each independently is selected from a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 aralkyl group, -OR b and -OC(=O)R c ,

[0051] R 4 to R 6 at least one of which is selected from -OR b and -OC(=O)R c ,

[0052] R b is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof, and

[0053] R c 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.

[0054] As an example, R 4 to R 6 can be selected from -OR b and -OC(=O)R c .

[0055] In the examples, the compound represented by Chemical Formula 1 includes -OR b or -OC(=O)R c as a ligand, so the pattern formed using the semiconductor photoresist composition containing the compound represented by Chemical Formula 1 can exhibit excellent ultimate resolution.

[0056] In the examples, -OR b or -OC(=O)R cThe ligand can determine the solubility of the compound represented by Chemical Formula 1 in a solvent.

[0057] R 3 can be a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C4-C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof.

[0058] R b can be a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof, and

[0059] R c can be hydrogen, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

[0060] R 3 can be methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, formyl, acetyl, propionyl, butyryl, valeryl, ethoxy, propoxy, or a combination thereof.

[0061] R b can be ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or a combination thereof, and

[0062] R c can be hydrogen, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or a combination thereof.

[0063] A semiconductor photoresist composition can form patterns with high aspect ratios without pattern collapse. In embodiments, to form fine patterns having widths, for example, of about 5 nanometers to about 100 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 70 nanometers, about 5 nanometers to about 50 nanometers, about 5 nanometers to about 40 nanometers, about 5 nanometers to about 30 nanometers, or about 5 nanometers to about 20 nanometers, the semiconductor photoresist composition can be used in a lithography process using light having a wavelength range from about 5 nanometers to about 150 nanometers, such as about 5 nanometers to about 100 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 50 nanometers, about 5 nanometers to about 30 nanometers, or about 5 nanometers to about 20 nanometers. Thus, a semiconductor photoresist composition according to one embodiment can be used to implement extreme ultraviolet lithography using an EUV light source that provides light having a wavelength of about 13.5 nanometers.

[0064] A method of forming a pattern according to some embodiments includes coating a semiconductor photoresist composition comprising an organotin compound on a substrate; drying and heating to form a photoresist film; and exposing and developing the photoresist film, wherein the organotin compound has at least one organic ligand containing an Sn-C bond and at least one organic carbonyloxy group, and the photoresist film contains, before or after exposure, a compound represented by (R 1 Sn) x O y (OAR 2 ) z (wherein x, y, and z are each independently 0.1 to 0.9, x + y + z = 1, A is a single bond (e.g., a single covalent bond) or C=O, R 1 is selected from substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C6 to C30 aralkyl, and L a -O-R a (wherein L a is a substituted or unsubstituted C1 to C20 alkylene and R a is a substituted or unsubstituted C1 to C20 alkyl), and R 2 is hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof).

[0065] As an example, the fabricated pattern can be a photoresist pattern.

[0066] The photoresist film can include Sn-OAR 2A bond, Sn-O-Sn bond and / or Sn-C bond.

[0067] Before exposure, the content of the compound represented by (R 1 Sn) x O y (OAR 2 ) z contained in the photoresist film can be about 5 to about 95 wt% based on 100 wt% of the composition for semiconductor photoresist.

[0068] After exposure and development, the content of the compound represented by (R 1 Sn) x O y (OAR 2 ) z contained in the photoresist film can be about 5 to about 95 wt% based on 100 wt% of the semiconductor photoresist composition.

[0069] As an example, R 1 can be a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C4-C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof, and

[0070] R 2 can be hydrogen, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

[0071] As an example, R 1 can be methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, formyl, acetyl, propionyl, butyryl, valeryl, ethoxy, propoxy, or a combination thereof, and

[0072] R 2 can be hydrogen, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or a combination thereof.

[0073] Refer to the following Figures 1 - 5A method of forming a pattern using a semiconductor photoresist composition is described. Figures 1 - 5 FIG. is a cross-sectional view showing a method of forming a pattern using a semiconductor photoresist composition according to an embodiment of the present disclosure.

[0074] Referring Figure 1 , an object for etching is prepared. The object for etching may be a thin film 102 on a semiconductor substrate 100. Hereinafter, the object for etching is limited to the thin film 102, but the present disclosure is not limited thereto. The surface of the thin film 102 is cleaned to remove impurities and / or the like remaining thereon. The thin film 102 may be, for example, a silicon nitride layer, a polysilicon layer, and / or a silicon oxide layer.

[0075] Subsequently, a bottom resist composition for forming a bottom resist 104 is spin-coated on the surface of the cleaned thin film 102. However, the present disclosure is not limited thereto, and various suitable coating methods may be used, such as spraying, dip coating, knife coating, printing methods (such as inkjet printing and / or screen printing), and / or the like.

[0076] The coating process of the bottom resist may be omitted, and the following description includes the process of coating the bottom resist.

[0077] The coated composition is dried and baked to form a bottom resist 104 on the thin film 102. The baking may be performed at about 100°C to about 500°C, for example, about 100°C to about 300°C.

[0078] The bottom resist 104 is located between the substrate 100 and the photoresist film 106 ( Figure 2 ), so non-uniformity can be prevented or reduced, and the pattern formation ability of the photoresist line width can be improved by avoiding or reducing the scattering of rays reflected from the interface or interlayer between the substrate 100 and the photoresist film 106 into the unintended photoresist area.

[0079] Referring Figure 2 , a photoresist film 106 is formed by coating a semiconductor photoresist composition on the bottom resist 104. By coating the above semiconductor photoresist composition on the thin film 102 on the substrate 100 and then curing it by heat treatment, a photoresist film 106 is obtained.

[0080] In an embodiment, the coating of the semiconductor photoresist composition includes coating the semiconductor photoresist composition on the substrate 100 on which the thin film 102 is formed by a deposition method selected from chemical vapor deposition (CVD) and physical vapor deposition (PVD) and / or a coating method selected from spin coating, slot coating, and inkjet printing, and may include drying the coated semiconductor photoresist composition to form a photoresist film 106.

[0081] A semiconductor photoresist composition may include an organotin compound having at least one organic ligand containing an Sn-C bond and at least one organic carbonyloxy group.

[0082] According to some embodiments, a semiconductor photoresist composition may include the above organotin compound and a solvent, and may further include a resin.

[0083] The solvent contained in the semiconductor photoresist composition may be an organic solvent, such as an aromatic compound (e.g., xylene, toluene, etc.), an alcohol (e.g., 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropyl alcohol, 1-propanol, etc.), an ether (e.g., anisole, tetrahydrofuran, etc.), an ester (n-butyrate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, etc.), a ketone (e.g., methyl ethyl ketone, 2-heptanone, etc.), or a mixture thereof, but not limited thereto.

[0084] The resin may be a phenolic resin containing at least one group 1 aromatic group.

[0085] Group 1

[0086]

[0087] The resin may have a weight average molecular weight of about 500 to about 20,000.

[0088] The resin may be included in an amount of about 0.1 wt% to about 50 wt% based on the total amount of the semiconductor photoresist composition.

[0089] If the resin is included in the above content range, it may have excellent etching resistance and heat resistance.

[0090] In an embodiment, the semiconductor photoresist composition may be composed of the above organometallic compound, solvent, and resin.

[0091] The semiconductor photoresist composition may further include additives as needed. Examples of additives may be a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quenching agent, or a combination thereof.

[0092] The surfactant may include, for example, an alkylbenzene sulfonate, an alkylpyridinium salt, polyethylene glycol, a quaternary ammonium salt, or a combination thereof, but not limited thereto.

[0093] The crosslinking agent can be, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, an acrylic acid-based crosslinking agent, an epoxy-based crosslinking agent, and / or a polymer-based crosslinking agent, but is not limited thereto. The crosslinking agent can have at least two substituents that form crosslinks. For example, compounds such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, methyl acrylate, 1,4-butanediol diglycidyl ether, glycidol, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, trimethylolpropane triglycidyl ether, 1,3-bis(glycidyloxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, and / or methoxymethylated thiourea, and / or analogs.

[0094] The leveling agent can be used to improve the flatness of the coating during the printing process and can be any suitable commercially available leveling agent.

[0095] The organic acid can include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, fluorinated sulfonate, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or a combination thereof, but is not limited thereto.

[0096] The quenching agent can be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0097] The usage amount of the additive can be controlled according to the appropriate or desired performance.

[0098] In an embodiment, the semiconductor photoresist composition may further include a silane coupling agent as an adhesion enhancer to improve the close contact force with the substrate (e.g., to improve the adhesion of the semiconductor photoresist composition to the substrate). The silane coupling agent may be, for example, a silane compound containing a carbon-carbon unsaturated bond, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane; and / or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyl diethoxysilane; trimethoxy[3-(phenylamino)propyl]silane, and / or the like, but not limited thereto.

[0099] Subsequently, the substrate 100 with the photoresist film 106 is subjected to a first baking process. The first baking process may be performed at about 80 °C to about 120 °C.

[0100] Referring Figure 3 , the photoresist film 106 may be selectively exposed using a patterned mask 110.

[0101] For example, the exposure may use actinic radiation including light having a high energy wavelength, such as EUV (extreme ultraviolet; wavelength of about 13.5 nm), electron beam (E-Beam), and / or the like, as well as wavelengths such as i-line (wavelength of about 365 nm), KrF excimer laser (wavelength of about 248 nm), ArF excimer laser (wavelength of about 193 nm), and / or the like.

[0102] For example, the light for exposure according to one embodiment may have a short wavelength range of about 5 nm to about 150 nm and a high energy wavelength, such as EUV (extreme ultraviolet; wavelength of about 13.5 nm), electron beam (E-Beam), and / or the like.

[0103] The exposed area 106a of the photoresist film 106 and the unexposed area 106b of the photoresist film 106 have different solubilities, which is achieved by forming a polymer formed through a crosslinking reaction (such as a condensation reaction) between organometallic compounds.

[0104] Subsequently, the substrate 100 undergoes a second baking process. The second baking process can be performed at a temperature of about 90°C to about 200°C. Due to the second baking process, the exposed area 106a of the photoresist film 106 becomes insoluble in the developer.

[0105] In Figure 4 , a developer is used to dissolve and remove the unexposed area 106b of the photoresist film to form a photoresist pattern 108. In an embodiment, the unexposed area 106b of the photoresist film is dissolved and removed by using an organic solvent (such as 2-heptanone and / or the like) to complete the photoresist pattern 108 corresponding to a negative tone image.

[0106] As described above, the developer used in the method of forming a pattern according to an embodiment can be an organic solvent. The organic solvent used in the method of forming a pattern according to an embodiment can be, for example, ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, and / or the like; alcohols such as 4-methyl-2-pentanol, 1-butanol, isopropyl alcohol, 1-propanol, methanol, and / or the like; esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, and / or the like; aromatic compounds such as benzene, xylene, toluene, and / or the like, or a combination thereof.

[0107] However, the photoresist pattern according to an embodiment is not limited to a negative tone image, but can be formed to have a positive tone image. In an embodiment, the developer for forming a positive tone image can be a quaternary ammonium hydroxide composition such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or a combination thereof.

[0108] As described above, exposure to light with high energy (such as EUV (extreme ultraviolet; wavelength of about 13.5 nm), electron beam (E-Beam), and / or the like) and light with a wavelength (such as i-line (wavelength of about 365 nm), KrF excimer laser (wavelength of about 248 nm), ArF excimer laser (wavelength of about 193 nm), and / or the like) can provide a photoresist pattern 108 with a thickness of about 5 nm to about 100 nm. For example, the photoresist pattern 108 can have a thickness width of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm.

[0109] In an embodiment, the photoresist pattern 108 may have a pitch, and the pitch may have a half pitch less than or equal to about 50 nanometers, for example, less than or equal to about 40 nanometers, for example, less than or equal to about 30 nanometers, for example, less than or equal to about 20 nanometers, or for example less than or equal to about 15 nanometers, and a line width roughness less than or equal to about 10 nanometers, less than or equal to about 5 nanometers, less than or equal to about 3 nanometers, or less than or equal to about 2 nanometers.

[0110] Subsequently, the underlying resist 104 is etched using the photoresist pattern 108 as an etch mask. Through this etching process, an organic film pattern 112 is formed. The organic film pattern 112 may also have a width corresponding to that of the photoresist pattern 108.

[0111] Refer to Figure 5 , and the exposed thin film 102 is etched by applying the photoresist pattern 108 as an etch mask. As a result, the thin film is formed into a thin film pattern 114.

[0112] The etching of the thin film 102 may be, for example, dry etching using an etching gas, and the etching gas may be, for example, CHF3, CF4, Cl2, BCl3, and / or a mixed gas thereof.

[0113] During the exposure process, the thin film pattern 114 formed using the photoresist pattern 108 formed by an exposure process performed using an EUV light source may have a width corresponding to that of the photoresist pattern 108. For example, the thin film pattern 114 may have a width of 5 nanometers to 100 nanometers equal to that of the photoresist pattern 108. For example, the thin film pattern 114 formed using the photoresist pattern 108 formed by an exposure process performed using an EUV light source may have a width of about 5 nanometers to about 90 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 70 nanometers, about 5 nanometers to about 60 nanometers, about 5 nanometers to about 50 nanometers, about 5 nanometers to about 40 nanometers, about 5 nanometers to about 30 nanometers, or about 5 nanometers to about 20 nanometers, or for example, have a width less than or equal to about 20 nanometers, the same as the width of the photoresist pattern 108.

[0114] According to some embodiments, a photoresist film used in the above-described patterning method is provided.

[0115] The photoresist film according to some embodiments may include a compound represented by (R 1 Sn) x O y (OAR 2 ) z (where x, y, and z are each independently 0.1 to 0.9, x + y + z = 1, A is a single bond (e.g., a single covalent bond) or C=O, R 1Selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aralkyl, and L a -O-R a (wherein L a is a substituted or unsubstituted C1-C20 alkylene and R a is a substituted or unsubstituted C1-C20 alkyl), and R 2 is hydrogen, a substituted or unsubstituted C1-C20 alkyl, a substituted or unsubstituted C3-C20 cycloalkyl, a substituted or unsubstituted C2-C20 alkenyl, a substituted or unsubstituted C2-C20 alkynyl, a substituted or unsubstituted C6-C30 aryl, or a combination thereof).

[0116] The photoresist film may have a thickness of about 5 nanometers to about 100 nanometers.

[0117] Hereinafter, embodiments of the present disclosure will be described in more detail by way of examples of the preparation of the above semiconductor photoresist composition. However, the technical features of the present disclosure are not limited by the following examples.

[0118] Synthesis of organometallic compounds

[0119] Synthesis Example 1

[0120] In a 250 ml two-necked round-bottom flask, 40.7 g of t-butylSnPh3 and 300 g of propionic acid were heated under reflux for 24 hours.

[0121] Unreacted propionic acid was removed under reduced pressure to obtain a compound represented by Chemical Formula 2.

[0122] Chemical Formula 2

[0123]

[0124] Synthesis Example 2

[0125] A compound represented by Chemical Formula 3 was obtained in the same manner as in Synthesis Example 1, but using butyric acid instead of propionic acid.

[0126] Chemical Formula 3

[0127]

[0128] Synthesis Example 3

[0129] The compound represented by Chemical Formula 4 was obtained in the same manner as in Synthesis Example 1, except that t-amylSnPh3 was used instead of t-butylSnPh3.

[0130] Chemical Formula 4

[0131]

[0132] Synthesis Example 4

[0133] The compound represented by Chemical Formula 5 was obtained in the same manner as in Synthesis Example 1, except that butyric acid was used instead of propionic acid and t-amylSnPh3 was used instead of t-butylSnPh3.

[0134] Chemical Formula 5

[0135]

[0136] Synthesis Example 5

[0137] 30 ml of anhydrous pentane was added to 10 g of t-amylSnCl3, and then the mixture was kept at 0 °C. 7.4 g of diethylamine and 6.1 g of ethanol were added thereto, and then the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the resulting product was filtered, concentrated, and dried under vacuum to obtain the compound represented by Chemical Formula 6.

[0138] Chemical Formula 6

[0139]

[0140] Preparation of Semiconductor Photoresist Composition

[0141] Examples 1 to 14 and Comparative Examples 1 to 9

[0142] The compounds represented by Chemical Formulas 2 to 6 of Synthesis Examples 1 to 5 and the compounds represented by Chemical Formulas 7 to 9 (obtained from Sigma-Aldrich) were dissolved in each of the compositions shown in Table 1 at a concentration of 3 wt%, and then filtered through a 0.1-μm polytetrafluoroethylene (PTFE) syringe filter to prepare a semiconductor photoresist composition.

[0143] Chemical Formula 7

[0144]

[0145] Chemical Formula 8

[0146]

[0147] Chemical Formula 9

[0148]

[0149] Table 1

[0150] Organometallic compound Solvent Example 1 Chemical formula 2 PGMEA Example 2 Chemical formula 2 PGME Example 3 Chemical formula 2 MIBC Example 4 Chemical formula 3 PGMEA Example 5 Chemical formula 3 PGME Example 6 Chemical formula 3 MIBC Example 7 Chemical formula 4 PGMEA Example 8 Chemical formula 4 PGME Example 9 Chemical formula 4 MIBC Example 10 Chemical formula 5 PGMEA Example 11 Chemical formula 5 PGME Example 12 Chemical formula 5 MIBC Example 13 Chemical formula 6 PGME Example 14 Chemical formula 6 MIBC Comparative Example 1 Chemical formula 7 PGMEA Comparative Example 2 Chemical formula 7 PGME Comparative Example 3 Chemical formula 7 MIBC Comparative Example 4 Chemical formula 8 PGMEA Comparative Example 5 Chemical formula 8 PGME Comparative Example 6 Chemical formula 8 MIBC Comparative Example 7 Chemical formula 9 PGMEA Comparative Example 8 Chemical formula 9 PGME Comparative Example 9 Chemical formula 9 MIBC

[0151] *PGMEA: Propylene glycol methyl ether acetate

[0152] *PGME: Propylene glycol methyl ether

[0153] *MIBC: 4-Methyl-2-pentanol

[0154] Evaluation: Sensitivity, LER (Line Edge Roughness), and Ultimate Resolution

[0155] Each composition for photoresist was spin-coated on a 200 mm circular silicon wafer at a speed of 1500 rpm for 30 seconds, baked at 110 °C for 60 seconds, and left standing at room temperature for 30 seconds. Subsequently, the wafer was exposed by dividing the exposure dose using an EUV light source (Lawrence Berkeley National Laboratory Micro Exposure Tool) to pattern it into various L / S (1 / 1) sizes, thereby obtaining a photoresist film. After exposure, it was fired at 170 °C for 60 seconds and then developed with a PGMEA solvent. Finally, it was fired at 150 °C for 60 seconds and then analyzed by scanning electron microscopy (SEM).

[0156] Sensitivity evaluation criteria

[0157] -A: Less than 100 mJ / cm 2

[0158] -B: Greater than or equal to 100 mJ / cm 2

[0159] Line edge roughness evaluation criteria

[0160] -○: Less than or equal to 2 nm

[0161] -△: Greater than 2 nm and less than or equal to 5 nm

[0162] -X: Greater than 5 nm

[0163] Ultimate resolution evaluation criteria

[0164] -A: Less than CD 10 nm

[0165] -B: Greater than or equal to CD 10 nm

[0166] Table 2

[0167]

[0168] Referring to the results in Table 2, compared with the patterns formed using the photoresist compositions for semiconductors according to Comparative Examples 1 to 9, the patterns formed using the photoresist compositions for semiconductors according to Examples 1 to 14 exhibit excellent sensitivity, LER, and resolution characteristics.

[0169] Previously, certain embodiments of the present disclosure have been described and illustrated. However, it is obvious to those of ordinary skill in the art that the present disclosure is not limited to the described embodiments, and various modifications and conversions can be made without departing from the spirit and scope of the present disclosure. Therefore, these modified or converted embodiments should not be understood separately from the technical ideas and aspects of the present disclosure, and the modified embodiments are within the scope of the appended claims of the present disclosure and their equivalents.

Claims

1. A method of forming a pattern, comprising: Coating a semiconductor photoresist composition containing an organotin compound on a substrate; Drying and heating to form a photoresist film; And Exposing and developing the photoresist film, Wherein the organotin compound has at least one organic ligand containing an Sn-C bond and at least one organic carbonyloxy group, and The photoresist film contains, before or after exposure, a compound represented by (R 1 Sn) x O y (OAR 2 ) z wherein x, y, and z are each independently from 0.1 to 0.9, x + y + z = 1, A is a single bond or C=O, R 1 is selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aralkyl, and L a -O-R a wherein L a is a substituted or unsubstituted C1-C20 alkylene, and R a is a substituted or unsubstituted C1-C20 alkyl, and R 2 is hydrogen, a substituted or unsubstituted C1-C20 alkyl, a substituted or unsubstituted C3-C20 cycloalkyl, a substituted or unsubstituted C2-C20 alkenyl, a substituted or unsubstituted C2-C20 alkynyl, a substituted or unsubstituted C6-C30 aryl, or a combination thereof.

2. The method of forming a pattern according to claim 1, wherein: The photoresist film contains Sn-OAR 2 bonds, Sn-O-Sn bonds and Sn-C bonds.

3. The method of forming a pattern according to claim 1, wherein: Before exposure, based on the semiconductor photoresist composition being 100 wt%, the content of the compound represented by (R 1 Sn) x O y (OAR 2 ) z in the photoresist film is 5 to 95 wt%.

4. The method of forming a pattern according to claim 1, wherein: After exposure and development, based on the semiconductor photoresist composition being 100 wt%, the content of the compound represented by (R 1 Sn) x O y (OAR 2 ) z in the photoresist film is 5 to 95 wt%.

5. The method of forming a pattern according to claim 1, wherein: Coating the semiconductor photoresist composition containing an organotin compound on the substrate is carried out by one method selected from the following: Deposition methods selected from chemical vapor deposition and physical vapor deposition, and Coating methods selected from spin coating, slot coating, and inkjet printing.

6. The method of forming a pattern according to claim 1, wherein: The exposure of the photoresist film is performed using light with a wavelength of 5 nm to 150 nm.

7. The method of forming a pattern according to claim 1, wherein: R 1 is a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C4-C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof, and R 2 is hydrogen, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

8. The method of forming a pattern according to claim 1, wherein: R 1 is methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, formyl, acetyl, propionyl, butyryl, valeryl, ethoxy, propoxy, or a combination thereof, and R 2 is hydrogen, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or a combination thereof.

9. The method of forming a pattern according to claim 1, wherein: The semiconductor photoresist composition further includes additives such as a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quenching agent, or a combination thereof.

10. A photoresist film comprising a compound represented by (R 1 Sn) x O y (OAR 2 ) z wherein x, y, and z are each independently from 0.1 to 0.9, x + y + z = 1, A is a single bond or C=O, R 1 is selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aralkyl, and L a -O-R a wherein L a is a substituted or unsubstituted C1-C20 alkylene, and R a is a substituted or unsubstituted C1-C20 alkyl, and R 2 is hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, or a combination thereof.

11. The photoresist film according to claim 10, wherein: The thickness of the photoresist film is 5 nm to 100 nm.

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