Composition for semiconductor photoresist and method for forming patterns using the same

Abstract

This invention provides a semiconductor photoresist composition that offers excellent storage stability while also exhibiting excellent sensitivity, and a pattern formation method using the same. [Solution] A semiconductor photoresist composition according to one embodiment comprises an organometallic compound, a diketone compound, an alcohol containing two or more hydroxyl groups, and a solvent.

Description

[Technical Field]

[0001] This document describes a semiconductor photoresist composition and a pattern formation method using the same. [Background technology]

[0002] EUV (extreme ultraviolet) lithography is attracting attention as one of the key technologies for manufacturing next-generation semiconductor devices. EUV lithography is a pattern formation technique that uses EUV light with a wavelength of 13.5 nm as the exposure light source. It has been demonstrated that EUV lithography can form extremely fine patterns (for example, less than 20 nm) in the exposure process of semiconductor device manufacturing.

[0003] The realization of extreme ultraviolet (EUV) lithography requires the development of compatible photoresists that can achieve spatial resolutions of 16 nm or less. Currently, traditional chemically amplified (CA) photoresists are striving to meet the specifications for resolution, photospeed, feature roughness, and line edge roughness (LER) for next-generation devices.

[0004] The intrinsic image blur caused by acid-catalyzed reactions in these polymer-type photoresists limits resolution at small feature sizes, a fact long known in electron beam lithography. Chemically amplified (CA) photoresists are designed for high sensitivity, but their typical elemental makeup lowers the absorbance of the photoresist at a wavelength of 13.5 nm, resulting in reduced sensitivity, which can be even more problematic under EUV exposure.

[0005] CA photoresists also suffer from roughness issues at small feature sizes, and experiments have confirmed that line edge roughness (LER) increases as the photospeed decreases, partly due to the nature of the acid-catalyzed process. Due to the shortcomings and problems of CA photoresists, the semiconductor industry has a demand for new types of high-performance photoresists.

[0006] In order to overcome the shortcomings of the chemically amplified organic photosensitive compositions described above, inorganic photosensitive compositions have been studied. Inorganic photosensitive compositions are mainly used for negative tone patterning that is resistant to removal by developer compositions through chemical modification via a non-chemical amplification mechanism. Inorganic compositions contain inorganic elements that have a higher EUV absorption rate compared to hydrocarbons, and are known to ensure sensitivity even with a non-chemical amplification mechanism, be less sensitive to the stochastic effect, and have fewer line edge roughness and defects.

[0007] Inorganic photoresists based on tungsten and tungsten peroxopolyacids mixed with niobium, titanium, and / or tantalum have been reported for use as radiation-sensitive materials for patterning (US5061599; H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298-300, 1986).

[0008] These materials have proven effective in patterning large features in bilayer configurations with deep UV, X-ray, and electron beam sources. More recently, impressive performance has been demonstrated when using cationic hafnium metal oxide sulfate (HfSOx) materials with a peroxo complexing agent to image 15 nm half-pitch (HP) by projection EUV lithography (US2011-0045406; JK Stowers, A. Telecky, M. Kocsis, BL Clark, DA Keszler, A. Grenville, CN Anderson, PP Naulleau, Proc. SPIE, 7969, 796915, 2011). This system exhibits the best performance of non-CA photoresists and has a light speed that approaches the requirements for a viable EUV photoresist. However, hafnium metal oxide sulfate materials containing peroxo-complexing agents have several practical drawbacks. Firstly, these materials are coated with a highly corrosive sulfuric acid / hydrogen peroxide mixture, resulting in poor shelf-life stability. Secondly, structural modifications to improve performance are not easily made as a composite mixture. Thirdly, they must be developed with extremely high concentrations of TMAH (tetramethylammonium hydroxide) solution, such as 25 wt%.

[0009] Recently, with the discovery that molecules containing tin exhibit excellent extreme ultraviolet absorption, active research has been conducted. In the case of organotin polymers, one of them, negative tone patterning that cannot be removed by an organic developing solution through crosslinking with an oxo bond to the peripheral chain while the alkyl ligand dissociates due to light absorption or secondary electrons generated thereby is possible. Although it has been confirmed that such organotin polymers have a dramatic improvement in sensitivity while maintaining resolution and line edge roughness, additional improvement in the patterning characteristics is required for commercialization.

Summary of the Invention

Problems to be Solved by the Invention

[0010] One embodiment provides a composition for a semiconductor photoresist that has excellent storage stability and excellent sensitivity.

[0011] Another embodiment provides a patterning method using the composition for a semiconductor photoresist.

Means for Solving the Problems

[0012] The composition for a semiconductor photoresist according to one embodiment contains an organometallic compound, a diketone compound, an alcohol containing two or more hydroxy groups, and a solvent.

Effects of the Invention

[0013] The composition for a semiconductor photoresist according to one embodiment has excellent storage stability and excellent sensitivity, and patterns formed using the composition for a semiconductor photoresist can achieve excellent resolution.

Brief Description of the Drawings

[0014] [Figure 1] It is a cross-sectional view for explaining a patterning method using the composition for a semiconductor photoresist according to one embodiment.

Modes for Carrying Out the Invention

[0015] Embodiments of the present invention will be described in detail below with reference to the attached drawings. However, in this description, explanations of functions or configurations that have already been made public will be omitted in order to clarify the gist of this description.

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

[0017] In the drawings, thicknesses were enlarged to clearly represent various layers and regions. Furthermore, for explanatory purposes, the thicknesses of some layers and regions were exaggerated in the drawings. When a layer, film, region, plate, or other part is described as being "on top of" or "on" another part, this includes not only cases where it is "directly on top of" another part, but also cases where another part lies in between.

[0018] In this description, "substituted" means that the hydrogen atom is replaced by deuterium, halogen group, hydroxyl group, carboxyl group, thiol group, cyano group, nitro group, -NRR' (where R and R' are independently hydrogen, a substituted or unsubstituted saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted saturated or unsaturated alicyclic hydrocarbon group having 3 to 30 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms), -SiRR'R'' (where R, R', and R'' are independently hydrogen, a substituted or unsubstituted This means that the group is substituted with an alkyl group having 1 to 30 carbon atoms, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group having 3 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, or a combination thereof. "Unsubstituted" means that the hydrogen atom remains as a hydrogen atom without being replaced by another substituent.

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

[0020] The alkyl group may be an alkyl group having 1 to 8 carbon atoms. For example, the alkyl group may be an alkyl group having 1 to 7 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. For example, the alkyl group having 1 to 5 carbon atoms may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group or a 2,2-dimethylpropyl group.

[0021] In this document, unless otherwise defined, "cycloalkyl group" refers to a monovalent cyclic aliphatic saturated hydrocarbon group.

[0022] The cycloalkyl group may be a cycloalkyl group having 3 to 8 carbon atoms, for example, a cycloalkyl group having 3 to 7 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. For example, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, but is not limited to these.

[0023] In this specification, “aryl group” means a substituent in which all elements of the cyclic substituent have p-orbitals, and these p-orbitals form a conjugation, and includes monocyclic or fusion-ring polycyclic (i.e., rings sharing adjacent pairs of carbon atoms) functional groups.

[0024] In this specification, a "heteroaryl group" means an aryl group containing at least one heteroatom selected from the group consisting of N, O, S, P, and Si. Two or more heteroaryl groups may be directly linked through sigma bonds, or, if the heteroaryl group contains two or more rings, the two or more rings may be fused together. If the heteroaryl group is a fused ring, each ring may contain one to three of the heteroatoms.

[0025] In this specification, "alkenyl group" means an aliphatic unsaturated alkenyl group, which is a linear or branched aliphatic hydrocarbon group containing one or more double bonds, unless otherwise defined.

[0026] In this specification, "alkynyl group" means an aliphatic unsaturated alkynyl group, which is a linear or branched aliphatic hydrocarbon group containing one or more triple bonds, unless otherwise defined.

[0027] A semiconductor photoresist composition according to one embodiment will be described below.

[0028] A semiconductor photoresist composition according to one embodiment comprises an organometallic compound, a diketone compound, an alcohol containing two or more hydroxyl groups, and a solvent.

[0029] A semiconductor photoresist composition according to one embodiment contains both ketone compounds and alcohol compounds, and can improve sensitivity by reducing the amount of ligand remaining in the photoresist produced from the composition. Since the ketone compounds and alcohol compounds have relatively high pKa values ​​and low boiling points compared to general acid additives, a composition containing all of these compounds can improve sensitivity while maintaining excellent storage stability.

[0030] The diketone compound is a compound containing two carbonyl groups, and may be, for example, acetylacetone, 1,1,1,5,5,5-Hexafluoro-pentane-2,4-dione, or 3-Chloro-2,4-pentanedione.

[0031] The aforementioned alcohol containing two or more hydroxyl groups means a compound containing two or more hydroxyl groups, for example, two to five, for example, two or three, and may be a dihydric alcohol, for example.

[0032] The alcohol containing two or more hydroxyl groups may be, for example, pinacol, propanediol, 2-hydroxymethyl-1,3-propanediol, or glycerol.

[0033] The diketone compound and the alcohol containing two or more hydroxyl groups may be present in a weight ratio of 5:95 to 60:40, for example, 5:95 to 55:45, 5:95 to 50:50, 5:95 to 60:40, 10:90 to 60:40, 10:90 to 55:45, or 10:90 to 50:50. The composition contains the diketone compound and the alcohol containing two or more hydroxyl groups within the above content ranges, which enhances storage stability while further improving the sensitivity of the photoresist.

[0034] The diketone compound is present in an amount of 0.1% to 10% by weight relative to 100% by weight of the semiconductor photoresist composition, for example, 0.1% to 10% by weight, 0.3% to 10% by weight, 0.5% to 10% by weight, 0.1% to 9% by weight, or 0.1% to 8% by weight. The presence of the diketone compound in the composition within these content ranges can further improve the storage stability of the composition.

[0035] The alcohol containing two or more hydroxyl groups is present in an amount of 0.1% to 10% by weight relative to 100% by weight of the semiconductor photoresist composition, for example, 0.1% to 10% by weight, 0.3% to 10% by weight, 0.5% to 10% by weight, 0.1% to 9% by weight, or 0.1% to 8% by weight. The composition contains alcohol containing two or more hydroxyl groups within the above content ranges to further improve the sensitivity of the photoresist.

[0036] The organometallic compound may be present in an amount of 0.5% to 30% by weight relative to 100% by weight of the semiconductor photoresist composition. The organometallic compound may be present in amounts of, for example, 1% to 30% by weight, 1% to 25% by weight, 1% to 20% by weight, 1% to 15% by weight, 1% to 10% by weight, or 1% to 5% by weight relative to 100% by weight of the semiconductor photoresist composition.

[0037] A semiconductor photoresist composition according to one embodiment can improve the sensitivity of a photoresist by containing the organometallic compound within the specified content range.

[0038] The organometallic compound may also be an organotin compound containing at least one organooxy group.

[0039] The aforementioned organometallic compound can be represented by the following chemical formula 1: [ka]

[0040] In the above chemical formula 1, R 1 This is selected from substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, and substituted or unsubstituted C7-C30 arylalkyl groups. R 2 ~R 4 Each of these independently comprises a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, an alkoxy, and an aryloxy (-OR) group. b , here R b (which is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), a carboxyl group (-O(CO)R c , R cis hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), an alkylamide or a dialkylamide (-NR d R e , where R d and R e are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), an amidato (-NR f (COR g ), where R f and R g are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), an amidinato (-NR h C(NR i )R j , where R h , R i , and R j are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), an alkylthio and an arylthio (-SR k , where R k(which is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof) or a thiocarboxyl group (-S(CO)R l , R l (These are hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof.) R 2 ~R 4 At least one of them is an alkoxy and an aryloxy (-OR b , here R b (The group is selected from among substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof.)

[0041] The aforementioned R 2 ~R 4 These are independently alkoxy and aryloxy (-OR) b , here R b The group can be selected from among substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof.

[0042] On the other hand, the compound represented by chemical formula 1 has -OR as a ligand. bBy including this, patterns formed using a semiconductor photoresist composition containing it can exhibit excellent limiting resolution.

[0043] Also, -OR b The ligand can determine the solubility of the compound represented by chemical formula 1 in a solvent.

[0044] The aforementioned R 1 This is selected from substituted or unsubstituted C1-C8 alkyl groups, substituted or unsubstituted C3-C8 cycloalkyl groups, substituted or unsubstituted C2-C8 alkenyl groups, substituted or unsubstituted C2-C8 alkynyl groups, substituted or unsubstituted C6-C20 aryl groups, and substituted or unsubstituted C7-C20 arylalkyl groups. R b This may 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.

[0045] The aforementioned R 1 These are methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, or combinations thereof. R b This may be an ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, or a combination thereof.

[0046] In addition to the organometallic compound, diketone compound, alcohol containing two or more hydroxyl groups, and solvent, the semiconductor resist composition according to one embodiment may further contain a resin.

[0047] The aforementioned resin may be a phenolic resin containing at least one of the aromatic molecules listed in Group 2 below.

[0048] [ka]

[0049] The resin may have a weight-average molecular weight of 500 g / mol to 20,000 g / mol.

[0050] On the other hand, the semiconductor photoresist composition preferably consists of the aforementioned organometallic compound, diketone compound, alcohol containing two or more hydroxyl groups, solvent, and resin.

[0051] The solvent contained in the semiconductor photoresist composition according to one embodiment may be an organic solvent, and may include, but is not limited to, aromatic compounds (e.g., xylene, toluene), alcohols (e.g., 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropyl alcohol, 1-propanol), ethers (e.g., anisole, tetrahydrofuran), esters (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate), ketones (e.g., methyl ethyl ketone, 2-heptanone), and mixtures thereof.

[0052] The semiconductor photoresist compositions according to the embodiments described above may optionally further include additives. Examples of such additives include surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0053] The surfactant may be, but is not limited to, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts, or combinations thereof.

[0054] Examples of crosslinking agents include, but are not limited to, melamine-based crosslinking agents, substituted urea-based crosslinking agents, acrylic-based crosslinking agents, epoxy-based crosslinking agents, or polymer-based crosslinking agents. Crosslinking agents having at least two crosslinking substituents can be used, such as compounds like methoxymethylated glycolyl, butoxymethylated glycolyl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, acrylic methacrylate, 1,4-butanediol diglycidyl ether, glycidol, diglycidyl 1,2-cyclohexane dicarboxylate, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea.

[0055] Leveling agents are used to improve coating flatness during printing, and commercially available, known leveling agents can be used.

[0056] The organic acids may be, but are not limited to, p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, fluorinated sulfonium salts, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or combinations thereof.

[0057] The quencher may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0058] The amount of these additives used can be easily adjusted according to the desired physical properties, and they can also be omitted.

[0059] Furthermore, the semiconductor photoresist composition may be further enhanced with a silane coupling agent as an adhesive enhancer to improve adhesion to the substrate (for example, to improve the adhesion of the semiconductor photoresist composition to the substrate). The silane coupling agent may be, but is not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxpropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; or carbon-carbon unsaturated bond-containing silane compounds such as trimethoxy[3-(phenylamino)propyl]silane.

[0060] The semiconductor photoresist composition does not cause pattern collapse even when forming patterns with a high aspect ratio. Therefore, it can be used in photoresist processes using light with wavelengths of 5 nm to 150 nm, such as a photoresist process using light with wavelengths of 5 nm to 100 nm, such as a photoresist process using light with wavelengths of 5 nm to 100 nm, such as a photoresist process using light with wavelengths of 5 nm to 80 nm, such as a photoresist process using light with wavelengths of 5 nm to 50 nm, such as a photoresist process using light with wavelengths of 5 nm to 40 nm, such as a photoresist process using light with wavelengths of 5 nm to 30 nm, and such as a photoresist process using light with wavelengths of 5 nm to 20 nm, in order to form fine patterns with widths of 5 nm to 100 nm, such as a photoresist process using light with wavelengths of 5 nm to 80 nm, such as a photoresist process using light with wavelengths of 5 nm to 50 nm, such as a photoresist process using light with wavelengths of 5 nm to 30 nm, and such as a photoresist process using light with wavelengths of 5 nm to 20 nm. Therefore, by using a semiconductor photoresist composition according to one embodiment, extreme ultraviolet lithography using an EUV light source with a wavelength of approximately 13.5 nm can be realized.

[0061] On the other hand, according to another embodiment, a method for forming a pattern using the aforementioned semiconductor photoresist composition can be provided. For example, the manufactured pattern may be a photoresist pattern.

[0062] A pattern formation method according to one embodiment includes the steps of forming an etching target film on a substrate, applying the above-mentioned semiconductor photoresist composition on the etching target film to form a photoresist film, patterning the photoresist film to form a photoresist pattern, and etching the etching target film using the photoresist pattern as an etching mask.

[0063] The following describes a method for forming a pattern using the aforementioned semiconductor photoresist composition with reference to Figure 1. Figure 1 is a cross-sectional view illustrating a method for forming a pattern using the semiconductor photoresist composition according to the present invention.

[0064] Referring to Figure 1(a), first, the object to be etched is prepared. An example of the object to be etched may be a thin film 102 formed on a semiconductor substrate 100. The following explanation will only describe the case where the object to be etched is a thin film 102. The surface of the thin film 102 is cleaned to remove any contaminants remaining on the thin film 102. The thin film 102 may be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film.

[0065] Next, a resist underlayer forming composition for forming a resist underlayer 104 is coated onto the surface of the cleaned thin film 102 using a spin coating method. However, one embodiment is not necessarily limited to this, and various known coating methods, such as spray coating, dip coating, knife-edge coating, and printing methods, such as inkjet printing and screen printing, can also be used.

[0066] The above-mentioned resist underlayer coating process can be omitted, and the following description will focus on the case where the resist underlayer is coated.

[0067] Subsequently, a drying and baking process is performed to form a resist underlayer film 104 on the thin film 102. The baking process is carried out at approximately 100°C to approximately 500°C, for example, at approximately 100°C to approximately 300°C.

[0068] The resist underlayer 104 is formed between the substrate 100 and the photoresist film 106, and can prevent non-uniformity of the photoresist linewidth and interference with pattern formation when irradiation lines reflected from the interface between the substrate 100 and the photoresist film 106 or from the interlayer hard mask are scattered into unintended photoresist areas.

[0069] Referring to Figure 1(b), the aforementioned semiconductor photoresist composition is coated onto the resist underlayer film 104 to form a photoresist film 106. The photoresist film 106 may also be formed by coating the aforementioned semiconductor photoresist composition onto a thin film 102 formed on the substrate 100 and then curing it through a heat treatment process.

[0070] More specifically, the step of forming a pattern using a semiconductor photoresist composition may include the steps of applying the aforementioned semiconductor photoresist composition onto a substrate 100 on which a thin film 102 is formed by spin coating, slit coating, inkjet printing, etc., and drying the applied semiconductor photoresist composition to form a photoresist film 106.

[0071] Since the compositions for semiconductor photoresists have already been explained in detail, we will omit further explanation.

[0072] Next, a first baking step is performed in which the substrate 100 on which the photoresist film 106 is formed is heated. The first baking step can be performed at a temperature of approximately 80°C to approximately 120°C.

[0073] Referring to Figure 1(c), the photoresist film 106 is selectively exposed using a patterned mask 110.

[0074] As an example, examples of light that can be used in the exposure process include not only light such as the activation irradiation diagram i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), but also light with high energy wavelengths such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0075] More specifically, the exposure light in one embodiment may be light having a wavelength range of 5 nm to 150 nm, or it may be light having a high energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0076] The exposed region 106b in the photoresist film 106 forms a polymer through crosslinking reactions such as condensation between organometallic compounds, thereby acquiring different solubility from the unexposed region 106a of the photoresist film 106.

[0077] Next, a second baking step is performed on the substrate 100. The second baking step can be performed at a temperature of approximately 90°C to approximately 200°C. By performing the second baking step, the exposed region 106b of the photoresist film 106 becomes less soluble in the developer.

[0078] Figure 1(d) shows a photoresist pattern 108 formed by dissolving and removing the photoresist film 106a corresponding to the unexposed region using a developer. Specifically, the photoresist pattern 108 corresponding to the negative tone image is completed by dissolving and then removing the photoresist film 106a corresponding to the unexposed region using an organic solvent such as 2-heptanone.

[0079] As mentioned above, the developer used in the pattern formation method according to one embodiment may be an organic solvent. Examples of organic solvents used in the pattern formation method according to one embodiment include ketones such as methyl ethyl ketone, acetone, cyclohexanone, and 2-heptanone; alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, and methanol; esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, and butyrolactone; aromatic compounds such as benzene, xylene, and toluene; or combinations thereof.

[0080] However, the photoresist pattern according to one embodiment is not necessarily limited to being formed as a negative tone image, and may be formed to have a positive tone image. In this case, examples of developers that can be used to form a positive tone image include tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or quaternary ammonium hydroxide compositions such as combinations thereof.

[0081] As mentioned above, the photoresist pattern 108 formed by exposure with light having wavelengths such as i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm), and ArF excimer laser (wavelength 193nm), as well as high-energy light such as EUV (Extreme UltraViolet; wavelength 13.5nm) and E-Beam (electron beam), can have a width of thickness from 5nm to 100nm. For example, the photoresist pattern 108 can be formed with a thickness of 5nm to 90nm, 5nm to 80nm, 5nm to 70nm, 5nm to 60nm, 5nm to 50nm, 5nm to 40nm, 5nm to 30nm, and 5nm to 20nm.

[0082] On the other hand, the photoresist pattern 108 can have a half-pitch of about 50 nm or less, for example 40 nm or less, for example 30 nm or less, for example 20 nm or less, for example 15 nm or less, and a pitch having a line width roughness of about 10 nm or less, about 5 nm or less, about 3 nm or less, or about 2 nm or less.

[0083] Next, the photoresist pattern 108 is used as an etching mask to etch the resist underlayer film 104. The organic film pattern 112 is formed by the etching process described above. The formed organic film pattern 112 may also have a width corresponding to the photoresist pattern 108.

[0084] Referring to Figure 1(e), the photoresist pattern 108 is applied as an etching mask to etch the exposed thin film 102. As a result, the thin film is formed as a thin film pattern 114.

[0085] The thin film 102 can be etched, for example, by dry etching using an etching gas, and the etching gas can be, for example, CHF3, CF4, Cl2, BCl3, or a mixture thereof.

[0086] In the previously performed exposure process, the thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process using an EUV light source can have a width corresponding to that of the photoresist pattern 108. For example, it can have a width of 5 nm to 100 nm, the same as that of the photoresist pattern 108. For instance, the thin film pattern 114 formed by the exposure process using an EUV light source can have widths of 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, and 5 nm to 20 nm, similar to the photoresist pattern 108, and more specifically, it can be formed with a width of 20 nm or less. [Examples]

[0087] The present invention will be described in more detail below through examples relating to the manufacture of the semiconductor photoresist composition mentioned above. However, the technical features of the present invention are not limited by the following examples.

[0088] Synthesis of organometallic compounds Synthesis Example 1 Add 30 ml of anhydrous pentane to 10 g of t-AmylSnCl3, maintain the temperature at 0°C, then add 7.4 g of diethylamine and 6.1 g of ethanol, and stir at room temperature for 1 hour. Once the reaction is complete, filter, concentrate, and vacuum dry to obtain the compound represented by the following chemical formula 2.

[0089] [ka]

[0090] (Manufacturing of semiconductor photoresist compositions) Examples 1-7 and Comparative Examples 1-3 The organometallic compound, diketone compound, and alcohol compound obtained in Synthesis Example 1 are each dissolved in the solvent Propylene glycol methyl ether acetate at a concentration of 4.5 wt% in the weight ratios shown in Table 1 below. The mixture is then filtered through a 0.1 μm PTFE syringe filter to produce a semiconductor photoresist composition. Note that the weight ratios (wt%) shown in Table 1 represent the weight ratios of the organometallic compound, diketone compound, and alcohol compound in their total composition, and do not represent the weight-based content of the entire composition including the solvent.

[0091] [Table 1]

[0092] C1: Acetylacetone C2:2,3-Dimethylbutane-2,3-diol

[0093] Evaluation 1: Sensitivity evaluation A 200 mm circular silicon wafer with a surface coated with HMDS was spin-coated with the semiconductor photoresist compositions according to the above examples and comparative examples at 1,500 rpm for 30 seconds, baked at 110°C for 60 seconds (post-apply bake, PAB), and then left at room temperature (23±2°C) for 30 seconds to form a photoresist thin film. The thickness of the film after coating and baking was measured by polarimetric measurement (ellipsometry), and the measured thickness was approximately 24 nm.

[0094] Subsequently, a linear array with a width of 50 nm was projected onto the wafer coated with the photoresist composition using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). The pad exposure time was adjusted to ensure that the increasing EUV dose was applied to each pad.

[0095] Subsequently, the resist and substrate were exposed on a hot plate at 160°C for 120 seconds and then fired. The fired film was developed with PGMEA solvent to form a negative tone image. Finally, the process was completed by hot plate firing at 150°C for 2 minutes.

[0096] The residual resist thickness of exposed pads was measured using a polarization measurement method (Ellipsometer). The remaining thickness was measured for each exposure amount and graphed as a function of the exposure amount. Eop was measured for each type of resist and is shown in Table 2 below.

[0097] [Table 2]

[0098] Referring to Table 2 above, it can be confirmed that the photoresist composition according to the examples exhibits even better sensitivity than the photoresist composition according to the comparative examples.

[0099] Evaluation 2: Storage stability evaluation The semiconductor photoresist compositions produced in Examples 1 to 7 and Comparative Examples 1 to 3 were stored at room temperature for two weeks, after which the presence of precipitate was checked. A value of X indicates the presence of precipitate, and a value of ○ indicates the absence of precipitate. The results are shown in Table 3 below.

[0100] [Table 3]

[0101] Referring to Table 3 above, it was confirmed that the photoresist composition according to the above example did not form a precipitate even after being left at room temperature for two weeks, while the photoresist composition according to the comparative example did form a precipitate. Therefore, it can be seen that the photoresist composition according to the example has superior storage stability compared to the photoresist composition according to the comparative example.

[0102] Although specific embodiments of the present invention have been described and illustrated above, it is obvious to those with ordinary skill in the art that the present invention is not limited to the described embodiments and can be modified and transformed in various ways without departing from the spirit and scope of the invention. Therefore, such modifications or variations should not be understood individually from the technical spirit or viewpoint of the present invention, and the modified embodiments should be said to fall within the scope of the claims of the present invention. [Explanation of Symbols]

[0103] 100...Substrate, 102...Thin film, 104...Resist underlayer film, 106...Photoresist film, 106a...Unexposed region, 106b...Exposed region, 108...Photoresist pattern, 110...Patterned mask, 112...Organic film pattern, 114...Thin film pattern.

Claims

1. Organometallic compounds; Diketone compounds; Alcohols containing two or more hydroxyl groups; and A composition for semiconductor photoresists, comprising a solvent.

2. The semiconductor photoresist composition according to claim 1, wherein the alcohol containing two or more hydroxyl groups is a dihydric alcohol.

3. The semiconductor photoresist composition according to claim 1, wherein the diketone compound and the alcohol containing two or more hydroxyl groups are present in a weight ratio of 5:95 to 60:

40.

4. The semiconductor photoresist composition according to claim 1, wherein the diketone compound and the alcohol containing two or more hydroxyl groups are present in a weight ratio of 5:95 to 50:

50.

5. The semiconductor photoresist composition according to claim 1, wherein the diketone compound is contained in an amount of 0.1% to 10% by weight based on 100% by weight of the semiconductor photoresist composition.

6. The semiconductor photoresist composition according to claim 1, wherein the alcohol containing two or more hydroxyl groups is present in an amount of 0.1% to 10% by weight relative to 100% by weight of the semiconductor photoresist composition.

7. The semiconductor photoresist composition according to claim 1, wherein the diketone compound is one or more of acetylacetone, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, and 3-chloro-2,4-pentanedione.

8. The semiconductor photoresist composition according to claim 1, wherein the alcohol containing two or more hydroxyl groups is one or more of pinacol, propanediol, 2-hydroxymethyl-1,3-propanediol, and glycerol.

9. The semiconductor photoresist composition according to claim 1, further comprising an additive of a surfactant, a crosslinking agent, a leveling agent, an organic acid, an inhibitor (quencher), or a combination thereof.

10. The semiconductor photoresist composition according to claim 1, wherein the organometallic compound is an organotin compound containing at least one organooxy group.

11. The organometallic compound is represented by the following chemical formula 1, and is the semiconductor photoresist composition according to claim 1: 【Chemistry 1】 In the above chemical formula 1, R １ This is selected from substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, and substituted or unsubstituted C7-C30 arylalkyl groups. R ２ to R ４ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, alkoxy and aryloxy (—OR ｂ , where R ｂ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), a carboxyl group (—O(CO)R ｃ , R ｃ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), an alkylamide or dialkylamide (—NR ｄ R ｅ , where R ｄ and R ｅ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof), an amidato (—NR ｆ (COR ｇ ), where R ｆ and R ｇ Each of these is independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidinato (-NR ｈ C (NR ｉ ) R ｊ Here, R ｈ , R ｉ , and R ｊ Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (-SR ｋ Here, R ｋ (which is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof) or a thiocarboxyl group (-S(CO)R ｌ , R ｌ (These are hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof.) R ２ ~R ４ At least one of them is an alkoxy and an aryloxy (-OR ｂ Here, R ｂ (The group is selected from among substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof.)

12. The aforementioned R ２ ~R ４ These are independently alkoxy and aryloxy (-OR ｂ Here, R ｂ The semiconductor photoresist composition according to claim 11, wherein is selected from among 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.

13. The aforementioned R １ This is selected from substituted or unsubstituted C1-C8 alkyl groups, substituted or unsubstituted C3-C8 cycloalkyl groups, substituted or unsubstituted C2-C8 alkenyl groups, substituted or unsubstituted C2-C8 alkynyl groups, substituted or unsubstituted C6-C20 aryl groups, and substituted or unsubstituted C7-C20 arylalkyl groups. R ｂ The semiconductor photoresist composition according to claim 11, wherein is 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.

14. The step of forming the film to be etched on the substrate; A step of forming a photoresist film by applying a semiconductor photoresist composition according to any one of claims 1 to 13 onto the film to be etched; The step of patterning the photoresist film to form a photoresist pattern; and A pattern formation method comprising the step of etching a film to be etched using the aforementioned photoresist pattern as an etching mask.

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