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

Abstract

To provide a semiconductor photoresist composition that exhibits excellent sensitivity and improved stability, as well as a method of forming patterns using the same.SOLUTION: The present invention provides a semiconductor photoresist composition that includes an organometallic compound represented by Chemical Formula 1 and a solvent, as well as a method of forming patterns using the same. The details of Chemical Formula 1 are as described in the specification.SELECTED DRAWING: Figure 5

Description

[Technical Field]

[0001] The present invention relates to a semiconductor photoresist composition and a pattern formation method utilizing 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. EUV lithography has been demonstrated to be able to 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, while designed for high sensitivity, can sometimes experience further difficulties under EUV exposure, partly because their typical elemental makeup lowers the photoresist absorbance at a wavelength of 13.5 nm, resulting in reduced sensitivity.

[0005] CA photoresists also sometimes experience difficulties due to roughness issues with small feature sizes, and experiments have shown that line edge roughness (LER) increases due to a decrease in photospeed, 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] To overcome the shortcomings of the aforementioned chemically amplified organic photosensitive compositions, inorganic photosensitive compositions have been studied. Inorganic photosensitive compositions are mainly used for negative tone patterning, where chemical modification by non-chemical amplification mechanisms results in resistance to removal by developer compositions. Inorganic compositions contain inorganic elements that have a higher EUV absorption rate compared to hydrocarbons, ensuring sensitivity even with non-chemical amplification mechanisms. They are also less sensitive to the stochastic effect, resulting in lower line edge roughness and fewer defects.

[0007] Inorganic photoresists based on tungsten and peroxopolyacids of tungsten mixed with niobium, titanium, and / or tantalum have been reported for 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 are deep UV, X-ray, and electron beam sources and have been effective in patterning large features in bilayer configurations. More recently, impressive performance has been demonstrated when using cationic hafnium metal oxide sulfate (HfSOx) materials with a peroxo complexing agent to image a 15 nm half-pitch (HP) by projection EUV lithography (US2011-0045406; JKStowers, A.Telecky, M.Kocsis, BLClark, DAKEszler, A.Grenville, CNAnderson, PPNaulleau, 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, they are complex mixtures, making structural modifications for performance improvement difficult. Thirdly, they must be developed with extremely high concentrations of TMAH (tetramethylammonium hydroxide) solution, such as 25 wt%, or similar.

[0009] Recently, there has been active research into tin-containing molecules, as they are known to exhibit outstanding absorption of extreme ultraviolet light. In the case of organotin polymers, one such polymer, the alkyl ligand is dissociated by light absorption or the secondary electrons generated by it, and negative tone patterning is possible through crosslinking via oxo bonds with surrounding chains, preventing removal by organic developers. Such organotin polymers have shown a dramatic improvement in sensitivity while maintaining resolution and line edge roughness, but further improvements in the aforementioned patterning properties are necessary for commercialization. [Overview of the project] [Problems that the invention aims to solve]

[0010] One embodiment of the present invention provides a semiconductor photoresist composition that exhibits excellent sensitivity and improved stability.

[0011] Another embodiment of the present invention provides a pattern formation method using the semiconductor photoresist composition described above. [Means for solving the problem]

[0012] A semiconductor photoresist composition according to one embodiment of the present invention comprises an organometallic compound represented by the following chemical formula 1 and a solvent.

[0013] [ka]

[0014] In the above chemical formula 1, M is one of the tetravalent, pentavalent, and hexavalent metals. R 1 This includes 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 L a -ORa (Here, L a is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, and R a is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms), R 2 is a tert-butyl group, benzoyl group, pivaloyl group, acetyl group, tert-butyldiphenylsilyl group, tert-butyldimethylsilyl group, allyl group, tetrahydropyranyl group, methoxymethyl group, benzyl ether group, tert-butyl ether group, p-toluenesulfonyl group, 2-phenyl ether group, benzyl group, trifluoromethyl group, benzyl ester group, tert-butyl ester group, 9-fluorenylmethyl group or triphenylmethyl group, X is O-[L 1 -O] n2 (Here, L 1 is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a combination thereof, and n2 is one of the integers from 0 to 10), O-C(O)-[L 2 -C(O)O] n3 (Here, L 2 is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a combination thereof, and n3 is one of the integers from 0 to 10), N(R 3 )-[L 3 -N(R 4 )] n4 (Here, L 3 is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a combination thereof, R 3 and R 4Each 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, where n4 is one integer from 0 to 10), N(R 5 )C(O)-[L 4 -N(R 6 )C(O)] n5 (L here) 4 R is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a combination thereof. 5 and R 6 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, where n5 is one integer from 0 to 10), or N(R 7 )CN(R 8 )-[L 5 -N(R 9 )CN(R 10 )] n6 (L here) 5 R is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a combination thereof. 7 ~R 10 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, where n6 is one integer from 0 to 10. n1 and m1 are each independently one of the integers between 1 and 5. 4 ≤ n1 + m1 ≤ 6.

[0015] The aforementioned M may be one selected from Sn, Sb, I, Te, In, Ag, Ni, Bi, and Po.

[0016] The aforementioned M can be Sn.

[0017] The aforementioned R 1 is a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or L a -OR a (L here) a R is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms. a (where is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), X is O, OC(O), N(R 3 )(R here 3 (is hydrogen, substituted or unsubstituted C1-C10 alkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, substituted or unsubstituted C2-C10 alkenyl groups, substituted or unsubstituted C2-C10 alkynyl groups, substituted or unsubstituted C6-C20 aryl groups, or combinations thereof), N(R 5 )C(O)(R here 5 (where is a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof), or N(R 7 )CN(R 8 )(Here, R 7 and R 8Each of these can independently be a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

[0018] The aforementioned R 1 The group may be a 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, formyl group, acetyl group, propanoyl group, butanoyl group, pentanoyl group, ethoxy group, propoxy group, or a combination thereof.

[0019] The aforementioned R 3 ~R 10 Each of these can independently be hydrogen, 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.

[0020] The aforementioned organometallic compound may be one selected from the compounds listed in Group 1 below.

[0021] [ka] [ka] Based on 100% by weight of the semiconductor photoresist composition, the organometallic compound may be present in an amount of 1% to 30% by weight.

[0022] The semiconductor photoresist composition may further contain additives such as surfactants, crosslinking agents, leveling agents, or combinations thereof.

[0023] A pattern formation method according to another embodiment of the present invention includes the steps of: forming an etching target film on a substrate; applying the above-described 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.

[0024] The step of forming the photoresist pattern can use light with a wavelength of 5 nm to 150 nm.

[0025] The step of providing a resist underlayer film formed between the substrate and the photoresist film may further be included.

[0026] The photoresist pattern can have a width of 5 nm to 100 nm. [Effects of the Invention]

[0027] A semiconductor photoresist composition according to one embodiment of the present invention can provide a photoresist pattern with improved storage stability, moisture stability, and sensitivity. [Brief explanation of the drawing]

[0028] [Figure 1] This is a cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment. [Figure 2] This is a cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment. [Figure 3] This is a cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment. [Figure 4] This is a cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment. [Figure 5] This is a cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment. [Modes for carrying out the invention]

[0029] The embodiments of the present invention will be described in detail below with reference to the attached drawings. However, in order to clarify the gist of this description, explanations of functions or configurations that are already publicly known will be omitted.

[0030] To clearly explain this description, unnecessary explanatory parts have been omitted, and the same or similar components are denoted by the same reference numerals throughout the specification. Furthermore, the dimensions and thicknesses of each component shown in the drawings are arbitrarily shown for the sake of explanation, and this description is not necessarily limited to those shown.

[0031] In the drawings, the thicknesses were enlarged to clearly represent multiple layers and regions. Furthermore, for explanatory purposes, the thicknesses of some layers and regions were exaggerated in the drawings. When a layer, film, region, plate, or other part is said to be "on top of" another part, this includes not only cases where it is "directly on top" of another part, but also cases where there is another part in between.

[0032] In this document, "substituted" means that the hydrogen atom is replaced by deuterium, halogen group, hydroxyl group, thiol group, cyano group, nitro group, carbonyl 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 hydrogen atom is substituted with an 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, 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 is not substituted by another substituent and remains as a hydrogen atom.

[0033] 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.

[0034] The alkyl group may be an alkyl group having 1 to 10 carbon atoms. For example, the alkyl group may be an alkyl group having 1 to 8 carbon atoms, 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.

[0035] In this document, "cycloalkyl group" refers to a monovalent cyclic aliphatic saturated hydrocarbon group unless otherwise defined.

[0036] The cycloalkyl group may be a cycloalkyl group having 3 to 10 carbon atoms, for example, a cycloalkyl group having 3 to 8 carbon atoms, 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, but is not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

[0037] 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 fused-ring polycyclic (i.e., rings sharing adjacent pairs of carbon atoms) functional groups.

[0038] 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.

[0039] 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.

[0040] In the chemical formulas described herein, t-Bu represents a tert-butyl group.

[0041] The following describes a semiconductor photoresist composition according to one embodiment of the present invention.

[0042] A semiconductor photoresist composition according to one embodiment of the present invention comprises an organometallic compound represented by the following chemical formula 1 and a solvent.

[0043] [ka]

[0044] In the above chemical formula 1, M is one of the tetravalent, pentavalent, and hexavalent metals. R 1 This includes 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 L a -OR a (L here) a R is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms. a ( is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms), R 2 These are tert-butyl group, benzoyl group, pivaloyl group, acetyl group, tert-butyldiphenylsilyl group, tert-butyldimethylsilyl group, allyl group, tetrahydropyranyl group, methoxymethyl group, benzyl ether group, tert-butyl ether group, p-toluenesulfonyl group, 2-phenyl ether group, benzyl group, trifluoromethyl group, benzyl ester group, tert-butyl ester group, 9-fluorenylmethyl group, or triphenylmethyl group. X is O-[L 1 -O] n2 (L here) 1 (where n2 is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a combination thereof, and n2 is one integer from 0 to 10), OC(O)-[L 2 -C(O)O] n3 (L here) 2 (where n3 is a substituted or unsubstituted alkylene group with 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group with 6 to 30 carbon atoms, or a combination thereof, and n3 is one integer from 0 to 10), N(R 3)-[L 3 -N(R 4 )] n4 (L here) 3 R is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a combination thereof. 3 and R 4 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, where n4 is one integer from 0 to 10), N(R 5 )C(O)-[L 4 -N(R 6 )C(O)] n5 (L here) 4 R is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a combination thereof. 5 and R 6 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, where n5 is one integer from 0 to 10), or N(R 7 )CN(R 8 )-[L 5 -N(R 9 )CN(R 10 )] n6 (L here) 5 R is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a combination thereof. 7 ~R 10Each is 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, and n6 is one of the integers from 0 to 10), and n1 and m1 are each independently one of the integers from 1 to 5, 4 ≦ n1 + m1 ≦ 6.

[0045] The organometallic compound according to the present invention has a bulky structure when R 2 is substituted, and thus has excellent storage stability and resistance to moisture.

[0046] Also, during exposure, deprotection of the R 2 occurs, and condensation occurs with surrounding organometallic compound molecules via X to form clusters, thereby improving sensitivity and resolution.

[0047] As an example, M can be selected from Sn, Sb, I, Te, In, Ag, Ni, Bi, and Po.

[0048] As a specific example, M can be Sn.

[0049] As an example, R 1 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or L a -O-R a (where L a is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and R a is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), and X is O, O-C(O), N(R3 )(Here, R 3 is hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof), N(R 5 )(where R 5 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof), or N(R 7 )C-N(R 8 )(where R 7 and R 8 are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof).

[0050] As a specific example, the above R 1 can be a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propenyl group, a butenyl group, an ethynyl group, a propynyl group, a butynyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pentanoyl group, an ethoxy group, a propoxy group, or a combination thereof).

[0051] As a specific example, the above R 3 ~R 10Each of these can independently be hydrogen, 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.

[0052] The aforementioned organometallic compound may be one selected from the compounds listed in Group 1 below.

[0053] [ka] [ka] The aforementioned organometallic compound strongly absorbs extreme ultraviolet light at 13.5 nm and exhibits excellent sensitivity to high-energy light.

[0054] In one embodiment of a semiconductor photoresist composition, the organometallic compound may be contained in an amount of 1% to 30% by weight, for example, 1% to 25% by weight, for example, 1% to 20% by weight, for example, 1% to 15% by weight, for example, 1% to 10% by weight, for example, 1% to 5% by weight, based on 100% by weight of the semiconductor photoresist composition, and is not limited to these amounts. When the organometallic compound is contained in an amount within the above range, the storage stability and etching resistance of the semiconductor photoresist composition are improved, and the resolution characteristics are improved.

[0055] A semiconductor photoresist composition according to one embodiment of the present invention, by containing the organometallic compound, can provide a semiconductor photoresist composition having excellent sensitivity and stability.

[0056] The solvent contained in the semiconductor resist composition according to one embodiment is 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.

[0057] In one embodiment, the semiconductor resist composition may further contain a resin in addition to the organometallic compound and the solvent.

[0058] The aforementioned resin may be a phenolic resin containing at least one of the aromatic molecules listed in Group 2 below.

[0059] [ka] The resin may have a weight-average molecular weight of 500 to 20,000.

[0060] The resin may be included in an amount of 0.1% to 50% by weight relative to the total content of the semiconductor resist composition.

[0061] When the aforementioned resin is included within the above-mentioned content range, it can have excellent etching resistance and heat resistance.

[0062] On the other hand, a semiconductor resist composition according to one embodiment preferably comprises the organometallic compound, solvent, and resin. However, the semiconductor resist composition according to the above-described embodiment may further contain additives. Examples of such additives include surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0063] The surfactant may be, but is not limited to, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts, or combinations thereof.

[0064] 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. Examples of crosslinking agents having at least two crosslinking substituents include compounds such as 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.

[0065] Leveling agents are used to improve coating flatness during printing, and commercially available, known leveling agents can be used.

[0066] Organic acids may include, but are not limited to, p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, sulfonium fluoride salts, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or combinations thereof.

[0067] The quencher may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0068] The amount of these additives used can be easily adjusted according to the desired physical properties, and they can also be omitted.

[0069] Furthermore, the semiconductor photoresist composition may be further enhanced with a silane coupling agent as an adhesion enhancer to improve adhesion to the substrate (for example, to improve the adhesion strength of the semiconductor resist 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-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; or carbon-carbon unsaturated bond-containing silane compounds such as trimethoxy[3-(phenylamino)propyl]silane.

[0070] The semiconductor photoresist composition may not experience 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 30 nm, such as a photoresist process using light with wavelengths of 5 nm to 20 nm, for example, 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 830 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.

[0071] On the other hand, according to another embodiment, a method for forming a pattern using the semiconductor photoresist composition may be provided. For example, the manufactured pattern may be a photoresist pattern.

[0072] A pattern formation method according to one embodiment includes the steps of forming an etching target film on a substrate, applying the 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.

[0073] The following describes a method for forming a pattern using the semiconductor photoresist composition described above, with reference to Figures 1 to 5. Figures 1 to 5 are cross-sectional views illustrating a pattern formation method using the semiconductor photoresist composition according to the present invention.

[0074] Referring to Figure 1, first, the object to be etched is prepared. An example of the object to be etched is a thin film 102 formed on a semiconductor substrate 100. The following explanation will only cover 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.

[0075] Next, a resist underlayer forming composition is applied to the surface of the cleaned thin film 102 using a spin coating method to provide a resist underlayer 104. However, one embodiment is not necessarily limited thereto, 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.

[0076] The above-mentioned resist underlayer coating step can be omitted, and the following description will focus on the case where the resist underlayer is coated.

[0077] 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 to 500°C, for example, at approximately 100°C to 300°C.

[0078] The resist underlayer 104 is formed between the substrate 100 and the photoresist film 106. This prevents the scattering of irradiation lines reflected from the interface between the substrate 100 and the photoresist film 106 or from the interlayer hard mask into unintended photoresist regions, thereby preventing non-uniformity of the photoresist linewidth and interference with pattern formation.

[0079] Referring to Figure 2, the semiconductor photoresist composition is coated onto the resist underlayer film 104 to form a photoresist film 106. The photoresist film 106 may be formed by coating the semiconductor photoresist composition onto a thin film 102 formed on the substrate 100 and then curing it by a heat treatment process.

[0080] More specifically, the step of forming a pattern using a semiconductor photoresist composition may include the steps of applying the 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.

[0081] Since the compositions for semiconductor photoresists have already been explained in detail, we will omit further explanation.

[0082] 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.

[0083] Referring to Figure 3, the photoresist film 106 is selectively exposed using a patterned mask 110.

[0084] As an example, examples of light that can be used in the exposure process include not only short-wavelength light such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), but also high-energy wavelength light such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0085] More specifically, the exposure light according to one embodiment may be short-wavelength light having a wavelength range of 5 nm to 150 nm, and may be light having a high-energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0086] The exposed regions 106a in the photoresist film 106 form polymers through crosslinking reactions such as condensation between organometallic compounds, resulting in different solubility from the unexposed regions 106a of the photoresist film 106.

[0087] 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 difficult to dissolve in the developer.

[0088] Figure 4 shows a photoresist pattern 108 formed by dissolving and removing the photoresist film 106a corresponding to the unexposed region using a developing solution. 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.

[0089] As described 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.

[0090] However, the photoresist pattern according to one embodiment is not necessarily limited to being formed as a negative tone image, but can also 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 quaternary ammonium hydroxide compositions such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof.

[0091] As described above, the photoresist pattern 108 formed by exposure with light having wavelengths such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), as well as high-energy light such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam), can have a width of 5 nm to 100 nm in thickness. As an example, the photoresist pattern 108 can be formed with 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, 5 nm to 20 nm, and 5 nm to 10 nm.

[0092] 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 10 nm or less, and a pitch having a line width roughness of about 5 nm or less, about 3 nm or less, about 2 nm or less, or about 1 nm or less.

[0093] Next, the photoresist pattern 108 is used as an etching mask to etch the resist underlayer film 104. This etching process forms an organic film pattern 112. The formed organic film pattern 112 can also have a width corresponding to the photoresist pattern 108.

[0094] Referring to Figure 5, 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.

[0095] 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.

[0096] The thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process using an EUV light source in the preceding exposure process can have a width corresponding to the photoresist pattern 108. For example, it can have a width of 5 nm to 100 nm, similar to 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]

[0097] The present invention will be described in more detail below through the examples of the manufacturing of the semiconductor photoresist composition described above. However, the technical features of the present invention are not limited by the following examples.

[0098] (Synthesis of organometallic compounds) Synthesis Example 1 10 g, 25.6 mmol of tert-butyltriphenyltin compound was gradually added dropwise with 25 ml of propionic acid at room temperature, and then heated under reflux at 110°C for 24 hours. After the temperature was lowered to room temperature, the propionic acid was vacuum distilled to obtain the compound represented by the following chemical formula 2.

[0099] [ka]

[0100] Synthesis Example 2 To the compound represented by chemical formula 2 obtained in Synthesis Example 1, mono-tert-butyl succinate was gradually added dropwise in an equivalent amount, and the mixture was stirred at room temperature for 24 hours to obtain the compound represented by the following chemical formula 3.

[0101] [ka]

[0102] Synthesis Example 3 The compound represented by the following chemical formula 4 was obtained by the same method as in Synthesis Example 2, except that mono-tert-butyl malonate was used instead of mono-tert-butyl succinate.

[0103] [ka]

[0104] Synthesis Example 4 The compound represented by the following chemical formula 5 was obtained by the same method as in Synthesis Example 2, except that 3-((tert-butyldimethylsilyl)oxy)-propanol was used instead of mono-tert-butyl succinate.

[0105] [ka]

[0106] Synthesis Example 5 The compound represented by the following chemical formula 6 was obtained by the same method as in Synthesis Example 2, except that an n-butyltriphenyltin compound was used instead of a tert-butyltriphenyltin compound.

[0107] [ka]

[0108] (Manufacturing of semiconductor photoresist compositions) Examples 1-3, Comparative Examples 1 and 2 The compounds represented by chemical formulas 2 to 6 obtained in synthesis examples 1 to 5 were each dissolved in 4-methyl-2-pentanol at a 3 wt% concentration, and the mixtures were filtered through a 0.1 μm PTFE syringe filter to produce photoresist compositions.

[0109] A 4-inch diameter circular silicon wafer with a native oxide surface was used as a substrate for thin-film deposition. Before depositing the resist thin film, the wafer was treated with a UV ozone cleaning system for 10 minutes. The resist composition was then spin-coated onto the wafer at 1500 rpm for 30 seconds, and the wafer was fired at 120°C for 120 seconds to form a thin film. Subsequently, the thickness of the coated and fired films was measured by polarization analysis (ellipsometry), and the results showed that the thickness was approximately 20 nm for Examples 1 to 3, Comparative Example 1, and Comparative Example 2.

[0110] Evaluation 1: Sensitivity evaluation A substrate coated with a resist thin film was exposed to an E-beam with an accelerating voltage of 100kV to form 40nm half-pitch nano-lines. After exposure at 40°C for 30 seconds, the irradiated substrate was immersed in a Petri dish containing 2-heptanone for 60 seconds, removed, washed with the same solvent for 10 seconds, and finally fired at 150°C. To confirm the pattern performance of the patterned substrate, the CD size of the formed lines was measured using FE-SEM (field emission scanning electron microscopy). The sensitivity was 1,000uC / cm². 2 For each energy level, a CD size of 40 nm or more is indicated by "◎", 35 nm or more by "○", and 35 nm or less by "△".

[0111] Evaluation 2: Evaluation of moisture stability To analyze the extent of the change caused by moisture, a tin compound was dissolved at a concentration of 10 wt% in 1-methyl-2-propyl acetate solvent containing 1 wt% water. Subsequently, the solution was... 119 Sn NMR measurements were performed, and the results were evaluated according to the following criteria and are shown in Table 1.

[0112] *Evaluation criteria ◎: No change in NMR peak ○: Change of 1-29% of the total integral value △: Change of 30-89% of the total integral value X: Change of more than 90% of the total integral value Evaluation 3: Storage stability evaluation The storage stability of the organometallic compounds used in Examples 1 to 3, Comparative Example 1, and Comparative Example 2 was evaluated according to the following criteria and is shown in Table 1 below.

[0113] [Storage stability] The semiconductor photoresist compositions prepared by Examples 1 to 3, Comparative Example 1, and Comparative Example 2 were left at room temperature (20±5℃) for a specified period. The degree of precipitation was then observed visually and evaluated according to the following storage criteria.

[0114] *Evaluation criteria ◎: Can be stored for 4 months or more. ○: Can be stored for 3 to less than 4 months. △: Can be stored for 1 to less than 3 months. X: Can be stored for less than 2 weeks.

[0115] [Table 1]

[0116] From the results in Table 1 above, it can be confirmed that the semiconductor photoresist composition according to the example exhibits superior sensitivity and significantly improved storage stability compared to the comparative example.

[0117] Although specific embodiments of the present invention have been described and illustrated above, it will be obvious to those ordinary skill in the art that the present invention is not limited to the described embodiments and can be modified and transformed in various ways without departing from the spirit and scope of the invention. Therefore, such modifications or variations should not be understood individually from the technical spirit or viewpoint of the present invention, and the modified embodiments can be said to fall within the scope of the claims of the present invention. [Explanation of Symbols]

[0118] 100...Substrate, 102...Thin film, 104...Resist underlayer film, 106...Photoresist film, 106a...Unexposed region, 106b...Exposed region, 108...Photoresist pattern, 112...Organic film pattern, 110...Patterned mask, 114...Thin film pattern.

Claims

1. Organometallic compounds represented by the following chemical formula 1; and Compositions for semiconductor photoresists containing a solvent: 【Chemistry 1】 In the aforementioned chemical formula 1, M is Sn, R １ This includes 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 L ａ -O-R ａ (Here L ａ R is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms. ａ (wherein is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms), R ２ These are tert-butyl group, benzoyl group, pivaloyl group, acetyl group, tert-butyldiphenylsilyl group, tert-butyldimethylsilyl group, allyl group, tetrahydropyranyl group, methoxymethyl group, benzyl ether group, tert-butyl ether group, p-toluenesulfonyl group, 2-phenyl ether group, benzyl group, trifluoromethyl group, benzyl ester group, tert-butyl ester group, 9-fluorenylmethyl group, or triphenylmethyl group. X is O-[L １ -O] ｎ２ (where L １ is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a combination thereof, and n2 is one of the integers from 1 to 10), or O-C(O)-[L ２ -C(O)O] ｎ３ (where L ２ is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a combination thereof, and n3 is one of the integers from 1 to 10), and n1 = 1, m1 = 3.

2. The aforementioned R １ is a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or L ａ -O-R ａ (Here L ａ R is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms. ａ The semiconductor photoresist composition according to claim 1, wherein ( is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms).

3. The aforementioned R １ The semiconductor photoresist composition according to claim 1, wherein is a 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, ethoxy group, propoxy group, or a combination thereof.

4. The semiconductor photoresist composition according to claim 1, wherein the organometallic compound is one selected from the compounds listed in Group 1 below: 【Chemistry 2】 【Transformation 3】

5. The semiconductor photoresist composition according to claim 1, wherein the organometallic compound is present in an amount of 1% to 30% by weight, based on 100% by weight of the semiconductor photoresist composition.

6. The semiconductor photoresist composition according to claim 1, further comprising an additive of a surfactant, a crosslinking agent, a leveling agent, or a combination thereof.

7. The steps include forming an etching target film on a substrate, The steps include applying the semiconductor photoresist composition according to any one of claims 1 to 6 onto the etchable film to form a photoresist film, The steps include: patterning the aforementioned photoresist film to form a photoresist pattern; A pattern formation method comprising the step of etching a film to be etched using the aforementioned photoresist pattern as an etching mask.

8. The pattern formation method according to claim 7, wherein the step of forming the photoresist pattern uses light with a wavelength of 5 nm to 150 nm.

9. The pattern forming method according to claim 7, further comprising the step of providing a resist underlayer film formed between the substrate and the photoresist film.

10. The pattern forming method according to claim 7, wherein the photoresist pattern has a width of 5 nm to 100 nm.

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