Semiconductor photoresist composition and method of forming pattern using the same

Abstract

A semiconductor photoresist composition and a method of forming a pattern using the same are provided. The semiconductor photoresist composition comprises an organometallic compound and a mixed solvent, wherein the mixed solvent comprises an alcohol compound and a non-alcohol compound in a weight ratio of about 1: 99 to about 30: 70.

Description

[0001] Citations of Related Applications

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2023-0155625 filed in the Korean Intellectual Property Office on November 10, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Embodiments of the present disclosure described herein relate to semiconductor photoresist compositions and methods of forming patterns using the same. Background Art

[0004] EUV (extreme ultraviolet) lithography is considered an important technology for manufacturing next-generation semiconductor devices. EUV lithography is a pattern forming technology that uses EUV rays having a wavelength of about 13.5 nm as an exposure light source. According to EUV lithography, it is known or believed that extremely fine patterns (e.g., less than or equal to about 20 nm) can be formed in an exposure process during semiconductor device manufacturing.

[0005] Extreme ultraviolet (EUV) lithography uses compatible photoresists that can be performed at a spatial resolution of less than or equal to about 16 nm. Currently, research or efforts are being made or conducted to address the specifications of comparable chemically amplified (CA) photoresists for next generation devices, such as resolution, photospeed, and feature roughness (or also known as line edge roughness or LER).

[0006] In polymer type or class photoresists, inherent image blurring due to acid catalysis limits resolution of small feature sizes. This limitation is known in electron beam (e-beam) lithography. Chemically amplified (CA) photoresists are designed for high sensitivity, but because their typical elemental composition reduces the absorbance of the photoresist at a wavelength of about 13.5 nm, and therefore reduces its sensitivity, chemically amplified (CA) photoresists may have more difficulties under EUV exposure.

[0007] In addition, CA photoresists may have difficulty with small feature sizes due to roughness issues, and experiments have shown that as the photospeed decreases due in part to the nature of the acid catalyst process, the line edge roughness (LER) of CA photoresists further increases. Therefore, due to these deficiencies and problems of CA photoresists, new high performance photoresists are desired or needed in the semiconductor industry.

[0008] In order to overcome the above-mentioned disadvantages of chemically amplified (CA) organic photosensitive compositions, inorganic photosensitive compositions have been studied or explored. The inorganic photosensitive compositions are mainly used for negative tone patterning, which is resistant to removal by a developer composition due to chemical modification by a non-chemical amplification mechanism. The inorganic composition contains an inorganic element having a higher EUV absorption rate than hydrocarbons, and thus can ensure sensitivity by a non-chemical amplification mechanism; in addition, the inorganic composition is less sensitive to stochastic effects, and thus can have low line edge roughness and a small number of defects.

[0009] Inorganic photoresists based on peroxypolyacids of tungsten mixed with tungsten, niobium, titanium and / or tantalum have been reported as radiation-sensitive materials for patterning (US 5061599; H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298-300, 1986), the entire contents of which are incorporated herein by reference.

[0010] These materials are effective for large spacing patterning of double-layer structures for ultraviolet (deep UV), X-ray and electron beam sources. Recently, if (for example, when) cationic hafnium metal oxide sulfate (HfSOx) materials are used together with peroxy complexing agents for imaging 15nm half pitch (HP) by projection EUV exposure, impressive performance has been obtained (US2011-0045406; JK Stowers, A. Telecky, M. Kocsis, BL Clark, DA Keszler, A. Grenville, CN Anderson, PP Naulleau, Proc. SPIE, 7969, 796915, 2011), the entire contents of which are incorporated herein by reference. The system exhibits the highest performance of non-CA photoresists and has a practical photosensitivity close to the requirements of EUV photoresists. However, hafnium metal oxide sulfate materials with peroxy complexing agents have some disadvantages. First, these materials are coated in a mixture of corrosive sulfuric acid / hydrogen peroxide and have insufficient shelf life stability. Second, as a complex mixture, its structural change for performance improvement is not easy. Third, development should be performed in a TMAH (tetramethylammonium hydroxide) solution at a very high concentration of about 25 wt% and / or the like.

[0011] Recently, active research has been conducted because it is known or believed that tin-containing molecules have excellent or suitable extreme ultraviolet light absorptivity. For organotin polymers in tin materials, alkyl ligands are dissociated by light absorption or secondary electrons generated thereby, and are cross-linked with adjacent chains through oxygen bonds, thereby enabling negative patterning that will not be removed by organic developers. That is, in other tin materials, these organotin polymers undergo dissociation of alkyl ligands due to light absorption or secondary electrons. These dissociated ligands are then cross-linked with adjacent polymer chains through oxygen bonds, thereby producing negative patterning that is still resistant to removal by organic developers. These organotin polymers exhibit greatly improved sensitivity and maintain resolution and line edge roughness, but for commercial applications or usability, the patterning features may still need to be further improved. Summary of the invention

[0012] An aspect according to one or more embodiments is directed to a semiconductor photoresist composition that improves problems occurring during spin coating.

[0013] An aspect according to one or more embodiments is directed to a method of forming a pattern using a semiconductor photoresist composition.

[0014] Aspects according to one or more embodiments are directed to a semiconductor photoresist composition that solves or eliminates the problems of surface roughness and coating defects occurring during spin coating.

[0015] Additional aspects will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the embodiments presented in the disclosure.

[0016] According to one or more embodiments, a semiconductor photoresist composition includes an organic metal compound and a mixed solvent, wherein the mixed solvent includes an alcohol compound and a non-alcohol compound in a weight ratio of about 1:99 to about 30:70, wherein the alcohol compound is included in an amount less than or equal to about 30 wt % based on the total weight (100 wt %) of the mixed solvent.

[0017] According to one or more embodiments, the method of forming a pattern includes forming an etching target layer on a substrate, coating the semiconductor photoresist composition on the etching target layer to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and etching the etching target layer using the photoresist pattern as an etching mask. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figures 1 to 5 Each of the diagrams is a cross-sectional view for explaining a method of forming a pattern using a semiconductor photoresist composition according to one or more embodiments.

[0019] Description of Reference Numerals

[0020] 100: substrate 102: film

[0021] 104: resist lower layer 106: photoresist layer

[0022] 106a: exposed area 106b: unexposed area

[0023] 108: Photoresist pattern 112: Organic layer pattern

[0024] 110: Patterned mask 114: Thin film pattern DETAILED DESCRIPTION

[0025] Hereinafter, with reference to the accompanying drawings, embodiments of the present disclosure will be described in more detail. In the following description of the present disclosure, some suitable functions or configurations will not be described in order to clarify the present disclosure.

[0026] As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items. As used herein, when preceding a list of elements, expressions such as "at least one of," "one of," and "selected from" modify the entire list of elements and do not modify a single element of the list. For example, "at least one of a, b, or c," "selected from at least one of a, b, and c," and the like may mean only a, only c, only c, both a and b (e.g., simultaneously), both a and c (e.g., simultaneously), both b and c (e.g., simultaneously), all of a, b, and c, or variations thereof.

[0027] In order to clearly illustrate the present disclosure, some descriptions and relationships may not be provided, and the same or similar structural elements are represented by the same reference numerals throughout the disclosure. In addition, since the size and thickness of each structure shown in the drawings are arbitrarily shown for better understanding and ease of description, the present disclosure is not necessarily limited thereto.

[0028] In the drawings, the thickness of layers, films, panels, regions, and / or the like are exaggerated for clarity. In the drawings, the thickness of a portion of a layer or region and / or the like is exaggerated for clarity. It will be understood that if (for example, when) an element such as a layer, film, region, or substrate is referred to as being "on" another element, it can be directly on the other element, or intervening elements may also be present.

[0029] As used herein, "substituted" means that a hydrogen atom is replaced by deuterium, halogen, hydroxyl, thiol, cyano, nitro, -NRR' (wherein R and R' can each independently be hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), -SiRR'R" (wherein R, R' and R" can each independently be The term "alkyl" refers to a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic 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, and / or a combination thereof (e.g., any suitable group). "Unsubstituted" means that a hydrogen atom is not replaced by another substituent and a hydrogen atom remains.

[0030] As used herein, if (eg, when) no definition is otherwise provided, "alkyl" refers to a straight or branched aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" without any double or triple bonds.

[0031] The alkyl group may be a C1 to C8 alkyl group. For example, the alkyl group may be a C1 to C7 alkyl group, a C1 to C6 alkyl group, or a C1 to C5 alkyl group. For example, the C1 to C5 alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or a 2,2-dimethylpropyl group.

[0032] As used herein, if (eg, when) no definition is otherwise provided, "cycloalkyl" refers to a monovalent cyclic aliphatic hydrocarbon group.

[0033] The cycloalkyl group may 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 may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, but the present disclosure is not limited thereto.

[0034] As used herein, "aliphatic unsaturated organic group" refers to a hydrocarbon group including bonds between carbon atoms in the molecule which are double bonds, triple bonds, and / or (eg, any suitable) combinations thereof.

[0035] The aliphatic unsaturated organic group can be a C2 to C8 aliphatic unsaturated organic group. For example, the aliphatic unsaturated organic group can be a C2 to C7 aliphatic unsaturated organic group, a C2 to C6 aliphatic unsaturated organic group, a C2 to C5 aliphatic unsaturated organic group or a C2 to C4 aliphatic unsaturated organic group. For example, the C2 to C4 aliphatic unsaturated organic group can 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.

[0036] As used herein, "aryl" refers to a substituent in which all atoms in a cyclic substituent have p-orbitals and the p-orbitals are conjugated, and may include monocyclic or fused-ring polycyclic functional groups (ie, rings that share adjacent pairs of carbon atoms).

[0037] As used in this article, "heteroaryl" may refer to an aryl group comprising at least one heteroatom selected from N, O, S, P and Si. Two or more heteroaryls are directly connected by a sigma bond, or if (for example, when) the heteroaryl includes two or more rings, the two or more rings may be fused. When the heteroaryl is a fused ring, each ring may include 1 to 3 heteroatoms.

[0038] As used herein, unless otherwise defined, "alkenyl" refers to an aliphatic unsaturated alkenyl group that is a straight or branched aliphatic hydrocarbon group containing at least one double bond.

[0039] As used herein, unless otherwise defined, "alkynyl" refers to an aliphatic unsaturated alkynyl group that is a straight or branched aliphatic hydrocarbon group containing at least one triple bond.

[0040] As used herein, the term "substantially" and similar terms are used as terms of approximation, rather than terms of degree, and are intended to account for the inherent deviations of measured or calculated values ​​that will be recognized by those of ordinary skill in the art. In addition, when used in conjunction with numerical values ​​or ranges of values ​​herein, the term "about" and similar terms include the specified value and values ​​within the acceptable deviation range of the specified value determined by those of ordinary skill in the art, taking into account the measurement in question and the errors associated with the measurement of the particular quantity (e.g., limitations of the measurement system). For example, "about" can mean within one or more standard deviations of the specified value, or within ±30%, 20%, 10%, 5% of the specified value.

[0041] In addition, any numerical range listed herein is intended to include all sub-ranges of the same numerical precision within the listed range. For example, the range of "1.0 to 10.0" is intended to include all sub-ranges between (and including) the listed minimum value of 1.0 and the listed maximum value of 10.0, i.e., having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, for example, 2.4 to 7.6. Any maximum numerical limit listed herein is intended to include all smaller numerical limits included therein, and any minimum numerical limit listed in this specification is intended to include all larger numerical limits included therein. Therefore, the applicant reserves the right to modify this specification (including claims) to explicitly list any sub-ranges within the range explicitly listed herein.

[0042] In the context of this application, unless otherwise defined, the terms "use", "using" and "used" may be considered synonymous with the terms "utilize", "utilizing" and "utilized", respectively. In addition, when describing embodiments of the present invention, the use of "may" refers to "one or more embodiments of the present invention".

[0043] Hereinafter, a semiconductor photoresist composition according to one or more embodiments is described.

[0044] According to one or more embodiments, a semiconductor photoresist composition includes an organic metal compound and a mixed solvent, wherein the mixed solvent includes an alcohol compound and a non-alcohol compound in a weight ratio of about 1:99 to about 30:70, wherein the alcohol compound is included in an amount less than or equal to about 30 wt % based on the total weight (100 wt %) of the mixed solvent.

[0045] The semiconductor photoresist composition should solve the problems of defects occurring during spin coating, such as surface roughness and coating defects, by including a mixed solvent, specifically, a mixed solvent including an alcohol compound.

[0046] In addition, the storage stability of the photoresist composition can be improved.

[0047] The mixed solvent included in the semiconductor photoresist composition according to one or more embodiments may include the alcohol compound and the non-alcohol compound in a weight ratio of about 5:95 to about 30:70.

[0048] As specific examples, the alcohol compound can be 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropanol, 1-propanol, propylene glycol monomethyl ether, 2-methyl-2-butanol, 2-butanol and / or their (e.g., any suitable) combinations.

[0049] For example, the non-alcohol compound may be an ether compound, an ester compound, a ketone compound, and / or (eg, any suitable) combination thereof.

[0050] As a specific example, the ether compound may be anisole, tetrahydrofuran, and / or (eg, any suitable) combination thereof.

[0051] As specific examples, the ester compound may be n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, and / or (eg, any suitable) combinations thereof.

[0052] As specific examples, the ketone compound may be methyl ethyl ketone, 2-heptanone, and / or (eg, any suitable) combinations thereof.

[0053] The organometallic compound may be included in an amount of about 1 wt % to about 30 wt % based on 100 wt % of the total weight of the semiconductor photoresist composition.

[0054] The semiconductor photoresist composition according to one or more embodiments includes the organic metal compound within the above content (eg, amount) range, thereby providing a semiconductor photoresist composition having excellent or suitable sensitivity.

[0055] The organic metal compound may include tin (Sn).

[0056] The organometallic compound may include at least one of an organooxy group or an organocarbonyloxy group.

[0057] The organometallic compound may be represented by Chemical Formula 1.

[0058] [Chemical formula 1]

[0059]

[0060] In Chemical Formula 1,

[0061] 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 arylalkyl and L a -OR a (where L a is a substituted or unsubstituted C1 to C20 alkylene group, and R a is a substituted or unsubstituted C1 to C20 alkyl group),

[0062] R 2 To R 4The alkyl radicals may be independently selected from substituted or unsubstituted C1 to C20 alkyl radicals, substituted or unsubstituted C3 to C20 cycloalkyl radicals, substituted or unsubstituted C2 to C20 alkenyl radicals, substituted or unsubstituted C2 to C20 alkynyl radicals, substituted or unsubstituted C6 to C30 aryl radicals, substituted or unsubstituted C6 to C30 arylalkyl radicals, -OR b and -OC(=O)R c ,

[0063] R 2 To R 4 At least one of (eg, selected from at least one of) is selected from -OR b and -OC(=O)R c ,

[0064] R b is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, and / or (e.g., any suitable) combination thereof, and

[0065] R c It is hydrogen, 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 and / or (e.g., any suitable) combinations thereof.

[0066] For example, R 2 To R 4 Can be selected from -OR b and -OC(=O)R c .

[0067] In one or more embodiments, the compound represented by Chemical Formula 1 includes -OR b or -OC(=O)R c As a ligand, a pattern formed using a semiconductor photoresist composition including the compound can exhibit excellent or suitable limiting resolution.

[0068] In addition, -OR b or -OC(=O)R c The ligand may determine the solubility of the compound represented by Chemical Formula 1 in a solvent.

[0069] R 1may be a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group including one or more double bonds or triple bonds, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C4 to C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group and / or (e.g., any suitable) combination thereof,

[0070] R b may be a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, and / or (e.g., any suitable) combination thereof, and

[0071] R c It can be hydrogen, substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 alkenyl, substituted or unsubstituted C2 to C8 alkynyl, substituted or unsubstituted C6 to C20 aryl and / or (e.g., any suitable) combinations thereof.

[0072] R 1 may 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 and / or (e.g., any suitable) combination thereof,

[0073] R b may be ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, and / or (e.g., any suitable) combination thereof, and

[0074] R c It may be hydrogen, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl and / or (e.g., any suitable) combination thereof.

[0075] The semiconductor photoresist composition according to one or more embodiments may further include a resin in addition to the above-mentioned organic metal compound and the mixed solvent.

[0076] The resin may be a phenolic resin including at least one aromatic moiety selected from Group 1.

[0077] [Group 1]

[0078]

[0079] The resin may have a weight average molecular weight of about 500 to about 20,000.

[0080] The resin may be included in an amount of about 0.1 wt % to about 50 wt % based on 100 wt % of the total amount (weight) of the semiconductor photoresist composition.

[0081] If the resin is included in the above content (eg, amount) range, the semiconductor photoresist composition may have excellent or suitable etching resistance and heat resistance.

[0082] In one or more embodiments, the semiconductor photoresist composition desirably consists of the above-mentioned organometallic compound, a mixed solvent, and a resin.

[0083] However, the semiconductor photoresist composition according to the above embodiment may further include additives as needed. Examples of the additives may be surfactants, crosslinking agents, leveling agents, organic acids, quenchers and / or (eg, any suitable) combinations thereof.

[0084] The surfactant may include, for example, alkylbenzene sulfonate, alkyl pyridinium salt, polyethylene glycol, quaternary ammonium salt, and / or (eg, any suitable) combination thereof, but the present disclosure is not limited thereto.

[0085] The cross-linking agent may be, for example, a melamine cross-linking agent, a substituted urea cross-linking agent, an acryl cross-linking agent, an epoxy cross-linking agent or a polymer cross-linking agent, but the present disclosure is not limited thereto. It may be a cross-linking agent having at least two cross-linking substituents, for example, such as the following compounds: methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, acryl methacrylate, 1,4-butanediol diglycidyl ether, glycidol, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea and / or the like.

[0086] The leveling agent may be used to improve the flatness of a coating layer during a printing process, and may be a commercially available suitable leveling agent.

[0087] The organic acid may include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalene disulfonic acid, methanesulfonic acid, fluorinated sulfonium salts, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, and / or (e.g., any suitable) combinations thereof, but the present disclosure is not limited thereto.

[0088] The quencher can be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, and / or (eg, any suitable) combinations thereof.

[0089] The amount of additives used can be controlled or selected according to the desired or suitable properties.

[0090] In addition, 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 including a carbon-carbon unsaturated bond, such as vinyl trimethoxysilane, vinyl triethoxysilane, vinyl trichlorosilane, vinyl tri(β-methoxyethoxy)silane; or 3-methacryloxypropyl trimethoxysilane, 3-acryloxypropyl trimethoxysilane, p-phenylyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane; trimethoxy [3- (phenylamino) propyl] silane and / or the like, but the present disclosure is not limited thereto.

[0091] Semiconductor photoresist composition can be formed into a pattern with a high aspect ratio and will not collapse. Therefore, in order to form a width of, for example, about 5nm to about 100nm, for example, about 5nm to about 80nm, for example, about 5nm to about 70nm, for example, about 5nm to about 50nm, for example, about 5nm to about 40nm, for example, about 5nm to about 30nm or for example, about 5nm to about 20nm fine pattern, semiconductor photoresist composition can be used for using wavelength in about 5nm to about 150nm, for example, about 5nm to about 100nm, about 5nm to about 80nm, about 5nm to about 50nm, about 5nm to about 30nm or about 5nm to about 20nm light lithography. Therefore, according to one or more embodiments of the semiconductor photoresist composition can be used to realize the EUV light source extreme ultraviolet lithography using about 13.5nm wavelength.

[0092] According to one or more embodiments, a method for forming a pattern using the semiconductor photoresist composition is provided. For example, the pattern produced may be a photoresist pattern.

[0093] The method of forming a pattern according to one or more embodiments includes forming an etch target layer on a substrate, coating the semiconductor photoresist composition on the etch target layer to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and etching the etch target layer using the photoresist pattern as an etching mask.

[0094] In the following, reference Figures 1 to 5 Methods of forming patterns using semiconductor photoresist compositions are described. Figures 1 to 5 is a cross-sectional view for explaining a method of forming a pattern using a semiconductor photoresist composition according to one or more embodiments.

[0095] refer to Figure 1 , an object for etching is prepared. The object for etching may be a thin film 102 formed on a semiconductor substrate 100. Hereinafter, the object for etching is limited to the thin film 102. 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, or a silicon oxide layer.

[0096] Subsequently, a resist underlayer composition for forming the resist underlayer 104 is spin-coated on the surface of the cleaned thin film 102. However, one or more embodiments are not limited thereto, and one or more suitable coating methods, for example, spray coating, dip coating, knife edge coating, printing (e.g., inkjet printing and screen printing), and / or the like may be used.

[0097] The coating process of the resist underlayer may not be required, that is, may be excluded or omitted, but hereinafter, a process including the coating of the resist underlayer is described.

[0098] Then, the applied composition is dried and baked to form a resist underlayer 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.

[0099] The resist lower layer 104 is formed between the substrate 100 and the photoresist layer 106, so if (for example, when) the rays reflected from the interface (on the interface) between the substrate 100 and the photoresist layer 106 or the hard mask (on the hard mask) between the layers are scattered to the unexpected photoresist area, the resist lower layer 104 can prevent or reduce the non-uniformity of the photoresist line width and improve the pattern formability. That is, the resist lower layer 104 is located between the substrate 100 and the photoresist layer 106. It is used to alleviate the non-uniformity of the photoresist line width and improve the pattern formability of the photoresist line width. Specifically, it helps to prevent the unexpected scattering of the rays reflected at the interface between the substrate 100 and the photoresist layer 106 or at the hard mask between the layers.

[0100] refer to Figure 2 The photoresist layer 106 is formed by coating a semiconductor photoresist composition on the resist underlayer 104. The photoresist layer 106 is obtained by coating the semiconductor photoresist composition on the thin film 102 formed on the substrate 100 and then curing it by heat treatment.

[0101] More specifically, pattern formation by using a semiconductor photoresist composition may include coating the semiconductor photoresist composition on the substrate 100 having the thin film 102 by spin coating, slit coating, inkjet printing, and / or the like, and then drying it to form a photoresist layer 106 .

[0102] The semiconductor photoresist composition has been described in detail and will not be described again.

[0103] Subsequently, a first baking process is performed on the substrate 100 having the photoresist layer 106. The first baking process may be performed at about 80°C to about 120°C.

[0104] refer to Figure 3 , the photoresist layer 106 may be selectively exposed using a patterned mask 110 .

[0105] For example, exposure can use activating radiation using: light with a high energy wavelength, such as EUV (extreme ultraviolet light; wavelength of about 13.5 nm), E-beam (electron beam) and / or the like; and light with a short 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.

[0106] More specifically, the light for exposure according to one or more embodiments may have a short wavelength in the range of about 5 nm to about 150 nm, or a high energy wavelength, for example, EUV (extreme ultraviolet light; wavelength of 13.5 nm), E-beam (electron beam), and / or the like. Specifically, in some embodiments, the light for exposure may have a short wavelength in the range of about 5 nm to 150 nm. In addition, it may include a high energy wavelength, such as EUV (extreme ultraviolet light), E-beam (electron beam), and / or the like having a wavelength of 13.5 nm.

[0107] The exposed region 106 a of the photoresist layer 106 forms a polymer through a cross-linking reaction such as condensation between organic metal compounds to have a different solubility from the unexposed region 106 b of the photoresist layer 106 .

[0108] Subsequently, a second baking process is performed on the substrate 100. The second baking process may be performed at a temperature of about 90° C. to about 200° C. Due to the second baking process, the exposed region 106 a of the photoresist layer 106 becomes less soluble to the developer.

[0109] exist Figure 4 In the process, the unexposed area 106b of the photoresist layer is dissolved and removed using a developer to form a photoresist pattern 108. For example, the unexposed area 106a of the photoresist layer is dissolved and removed using an organic solvent such as 2-heptanone and / or the like to complete the photoresist pattern 108 corresponding to the negative image.

[0110] As described above, the developer used in the method for forming a pattern according to one or more embodiments may be an organic solvent. The organic solvent used in the method for forming a pattern according to one or more embodiments may be, for example, a ketone such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, and / or the like; an alcohol such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, methanol, and / or the like; an ester such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, and / or the like; an aromatic compound such as benzene, xylene, toluene, and / or the like; and / or (for example, any suitable) combinations thereof.

[0111] However, the photoresist pattern according to one or more embodiments need not be limited to a negative image, but can be formed to have a positive image. In this article, the developer for forming the positive image can be a quaternary ammonium hydroxide composition, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and / or their (e.g., any suitable) combination.

[0112] As described above, exposure to light having high energy such as EUV (extreme ultraviolet light; wavelength of 13.5 nm), E-beam (electron beam) and / or the like and light having a short 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 having a width of about 5 nm to about 100 nm. For example, the photoresist pattern 108 may have a 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.

[0113] In contrast, the photoresist pattern 108 may have a half-pitch pitch of less than or equal to about 50 nm, e.g., less than or equal to about 40 nm, e.g., less than or equal to about 30 nm, e.g., less than or equal to about 20 nm, or e.g., less than or equal to about 15 nm, and a line width roughness of less than or equal to about 10 nm, less than or equal to about 5 nm, less than or equal to about 3 nm, or less than or equal to about 2 nm.

[0114] Subsequently, the photoresist pattern 108 is used as an etching mask to etch the resist lower layer 104. Through this etching process, an organic layer pattern 112 is formed. The organic layer pattern 112 may also have a width corresponding to the width of the photoresist pattern 108.

[0115] refer to Figure 5 , the exposed thin film 102 is etched by applying the photoresist pattern 108 as an etching mask. Thus, the thin film is formed into a thin film pattern 114.

[0116] 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, CHF 3 , CF 4 , Cl 2 , BCl 3 , and / or a mixed gas thereof.

[0117] The thin film pattern 114 formed by the photoresist pattern 108 formed by the exposure process using the EUV light source may have a width corresponding to the width of the photoresist pattern 108. For example, the thin film pattern 114 may have a width of about 5 nm to about 100 nm, which is equal to the width of the photoresist pattern 108. For example, the thin film pattern 114 formed by the photoresist pattern 108 formed by the exposure process using the EUV light source may have a 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 30 nm, or about 5 nm to about 20 nm, similar to the width of the photoresist pattern 108, and more specifically, a width less than or equal to about 20 nm.

[0118] Hereinafter, the present disclosure will be described in more detail through examples of the preparation of the above semiconductor photoresist composition. However, the present disclosure is not technically limited to the following examples.

[0119] Synthesis of organometallic compounds

[0120] Synthesis example 1

[0121] 40.7 g of tert-butyl SnPh3 and 300 g of propionic acid were added to a 250 mL two-necked round-bottom flask, and then heated to reflux for 24 hours.

[0122] By removing unreacted propionic acid therefrom under reduced pressure, a compound represented by Chemical Formula 2 is obtained.

[0123] [Chemical formula 2]

[0124]

[0125] Synthesis example 2

[0126] After adding 30 mL of anhydrous pentane to 10 g of tert-amyl SnCl3 and maintaining the temperature at 0°C, 7.4 g of diethylamine and 6.1 g of ethanol were added thereto, followed by stirring at room temperature for 1 hour. When the reaction was completed, the resultant was filtered, concentrated and vacuum dried to obtain a compound represented by Chemical Formula 3.

[0127] [Chemical formula 3]

[0128]

[0129] (Preparation of semiconductor photoresist composition)

[0130] Examples 1 to 3 and Comparative Examples 1 to 6

[0131] The compounds represented by Chemical Formulas 2 and 3 obtained in Synthesis Examples 1 and 2 were dissolved in a mixed solvent having a composition shown in Table 1 at a concentration of 3 wt %, and then filtered with a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to prepare a semiconductor photoresist composition.

[0132] Each photoresist composition was spin-coated at 1500rpm for 30 seconds on a 200mm circular silicon wafer with HMDS deposited on the surface, fired at 110°C for 60 seconds (post-baking (PAB) was applied), and then left to stand at room temperature for 30 seconds. Then, the silicon wafer was patterned to a size of 180nm L / S (1 / 1) using a KrF scanner to form a photoresist film. After exposure, it was baked at 170°C for 60 seconds and then developed with PGMEA solvent. Finally, after firing at 150°C for 60 seconds, the line width of the pattern (line) was measured using SEM (scanning electron microscope).

[0133] (Table 1)

[0134]

[0135]

[0136] *PGME: Propylene glycol monomethyl ether

[0137] *PGMEA: Propylene glycol monomethyl ether acetate

[0138] *MIBC: 4-methyl-2-pentanol

[0139] Evaluation 1: Surface roughness evaluation

[0140] The photoresist compositions according to Examples 1 to 3 and Comparative Examples 1 to 6 were spin-coated on the silicon wafer at 1500 rpm for 60 seconds, respectively, and baked at 110° C. for 60 seconds to form a thin film. The surface roughness of the thin film was measured from an image collected by an atomic force microscope (AFM) and / or the like using software (e.g., an optical profiler) according to the following criteria, and the results are shown in Table 2.

[0141] In surface roughness, the average roughness (R q ; Root mean square roughness) refers to the root mean square (rms) of the square of the vertical value within the reference length of the roughness profile.

[0142] [Evaluation criteria for surface roughness]

[0143] -○: Smaller than R q 0.4

[0144] -X: greater than or equal to R q 0.4

[0145] Evaluation 2: Storage stability evaluation

[0146] The photoresist compositions according to Examples 1 to 3 and Comparative Examples 1 to 6 were respectively spin-coated on silicon wafers at 1500 rpm for 60 seconds, baked at 110° C. for 60 seconds, exposed, and then baked at 170° C. for 60 seconds to make patterns. At this time, after confirming the sensitivity level (Eop / mJ) when forming the pattern, the sample was divided into three parts and stored at 5° C. (low temperature), 25° C. (room temperature) and 40° C. (high temperature). Afterwards, it was confirmed whether the initial sensitivity level was maintained at one-month intervals, and the results are shown in Table 2.

[0147] [Evaluation criteria for storage stability]

[0148] -○: After 2 months, the sensitivity change is less than 5%

[0149] -Δ: Sensitivity change is 5% or less within 1 month, and sensitivity change is 5% or more after 1 month

[0150] -X: Sensitivity change is 5% or more within 1 month

[0151] (Table 2)

[0152]

[0153]

[0154] According to the results in Table 2, patterns formed using the semiconductor photoresist compositions according to Examples 1 to 3 had improved coating properties compared to Comparative Examples 1 to 6.

[0155] In addition, under low temperature / room temperature / high temperature conditions, the storage stability of the semiconductor photoresist using the present disclosure is improved.

[0156] Any suitable hardware, firmware (e.g., an application specific integrated circuit), software, or a combination of software, firmware, and hardware may be used to implement a battery management system (BMS) device and / or any other related device or component according to an embodiment of the present invention described herein. For example, various components of the device may be formed on one integrated circuit (IC) chip or on different IC chips. In addition, various components of the device may be implemented on a flexible printed circuit film, a tape carrier package (TCP), a printed circuit board (PCB), or formed on a substrate. In addition, various components of the device may be processes or threads running on one or more processors in one or more computing devices, which execute computer program instructions and interact with other system components to perform various functions described herein. Computer program instructions are stored in a memory, which may be implemented in a computing device using a standard storage device such as a random access memory (RAM). Computer program instructions may also be stored in other permanent computer-readable media, such as a CD-ROM, a flash drive, and the like. In addition, those skilled in the art will recognize that without departing from the scope of the present disclosure, the functionality of various computing devices may be combined or integrated into a single computing device, or the functionality of a particular computing device may be distributed between one or more other computing devices.

[0157] Considering the overall content of the present disclosure, those skilled in the art will understand that each appropriate feature of the multiple embodiments according to the present disclosure can be partially or completely combined or combined with each other, and can be technically interlocked and operated in a variety of suitable ways, and each embodiment can be implemented independently of each other or in combination with each other in any suitable manner, unless otherwise described or indicated.

[0158] In the above, some embodiments of the present disclosure have been described and illustrated, but it is clear to those skilled in the art that the present disclosure is not limited to the one or more embodiments described, and they can be changed and transformed differently without departing from the spirit and scope of the present disclosure. Therefore, the embodiments thus changed or transformed cannot be understood separately from the technical ideas and aspects of the present disclosure, and the changed embodiments are within the scope of the claims of the present disclosure and their equivalents.

Claims

1. A semiconductor photoresist composition comprising: Organometallic compounds; and A mixed solvent comprising an alcohol compound and a non-alcohol compound in a weight ratio of 1:99 to 30:70, The alcohol compound is contained in an amount less than or equal to 30 wt % based on 100 wt % of the total weight of the mixed solvent.

2. The semiconductor photoresist composition according to claim 1, wherein The mixed solvent contains the alcohol compound and the non-alcohol compound in a weight ratio of 5:95 to 30:

70.

3. The semiconductor photoresist composition according to claim 1, wherein The alcohol compound is 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropanol, 1-propanol, propylene glycol monomethyl ether, 2-methyl-2-butanol, 2-butanol or a combination thereof.

4. The semiconductor photoresist composition according to claim 1, wherein The non-alcohol compound is an ether compound, an ester compound, a ketone compound or a combination thereof.

5. The semiconductor photoresist composition according to claim 4, wherein The ether compound includes anisole, tetrahydrofuran or a combination thereof, The ester compound includes n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate or a combination thereof, and The ketone compound includes methyl ethyl ketone, 2-heptanone or a combination thereof.

6. The semiconductor photoresist composition according to claim 1, wherein The organometallic compound may be included in an amount of about 1 wt % to about 30 wt % based on 100 wt % of the total weight of the semiconductor photoresist composition.

7. The semiconductor photoresist composition according to claim 1, wherein The semiconductor photoresist composition further comprises an additive of a surfactant, a cross-linking agent, a leveling agent, an organic acid, a quencher or a combination thereof.

8. The semiconductor photoresist composition according to claim 1, wherein The organometallic compound includes tin (Sn).

9. The semiconductor photoresist composition according to claim 1, wherein The organometallic compound includes at least one of an organooxy group or an organocarbonyloxy group.

10. The semiconductor photoresist composition according to claim 1, wherein The organometallic compound is represented by Chemical Formula 1: [Chemical formula 1] and In Chemical Formula 1, 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 arylalkyl and L a -OR a , where L a is a substituted or unsubstituted C1 to C20 alkylene group and R a is a substituted or unsubstituted C1 to C20 alkyl group, R 2 To R 4 are each independently 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 arylalkyl, -OR b and -OC(=O)R c , R 2 To R 4 At least one of -OR b and -OC(=O)R c , R b is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, and R c is hydrogen, 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, or a combination thereof.

11. The semiconductor photoresist composition according to claim 10, wherein R 1 is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C4 to C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof, R b is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, and R c It is hydrogen, substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 alkenyl, substituted or unsubstituted C2 to C8 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.

12. The semiconductor photoresist composition according to claim 10, 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, R b is ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or a combination thereof, and R c is hydrogen, ethyl, propyl, butyl, isopropyl, tert-butyl, 2,2-dimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, tolyl, xylyl, benzyl, or a combination thereof.

13. A method for forming a pattern, the method comprising: forming an etching target layer on a substrate; coating the semiconductor photoresist composition according to any one of claims 1 to 12 on the etching target layer to form a photoresist layer; patterning the photoresist layer to form a photoresist pattern; as well as The etch target layer is etched using the photoresist pattern as an etch mask.

14. The method according to claim 13, wherein The photoresist pattern is formed by using light having a wavelength of 5 nm to 150 nm.

15. The method according to claim 13, wherein The photoresist pattern has a width of 5 nm to 100 nm.

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