Semiconductor photoresist composition and pattern formation method using the same

Abstract

To provide a semiconductor photoresist composition with excellent coating properties, sensitivity, and pattern-forming abilities, and a method of forming patterns using the same.SOLUTION: A semiconductor photoresist composition includes an additive represented by chemical formula 1, and a solvent.SELECTED DRAWING: Figure 5

Description

[Technical Field]

[0001] The present invention relates to a semiconductor photoresist composition and a pattern forming method using the same. [Background technology]

[0002] EUV (extreme ultraviolet) lithography is attracting attention as one of the elemental technologies for manufacturing next-generation semiconductor devices. EUV lithography is a pattern formation technology 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 (e.g., 20 nm or less) during the exposure step in the semiconductor device manufacturing process.

[0003] The realization of extreme ultraviolet (EUV) lithography requires the development of compatible photoresists capable of achieving spatial resolution below 16 nm. Currently, traditional chemically amplified (CA) photoresists are being continuously refined to meet the specifications for resolution, optical speed, and feature roughness (line edge roughness or LER) for next-generation devices.

[0004] These chemically amplified photoresists generally contain organic polymers, but inherent image blurring due to acid-catalyzed reactions occurring in these chemically amplified photoresists limits resolution at small feature sizes, a fact long known in electron beam (e-beam) lithography. Chemically amplified (CA) photoresists were designed for high sensitivity, but their typical elemental composition reduces the photoresist's absorbance at 13.5 nm wavelengths, resulting in lower sensitivity and, in part, creating additional difficulties under EUV exposure.

[0005] CA photoresists can also suffer from roughness issues at small feature sizes, and experiments have shown that line edge roughness (LER) increases as the light speed decreases, due in part to the nature of the acid-catalyzed process. Due to the shortcomings and problems of CA photoresists, there is a demand in the semiconductor industry for a new class of high-performance photoresists.

[0006] To overcome the disadvantages of chemically amplified organic photoresists described above, inorganic photosensitive compositions have been researched. Inorganic photosensitive compositions are primarily used for negative-tone patterning, where chemical modification is achieved through a non-chemically amplified mechanism, making them resistant to removal by developer compositions. Inorganic photosensitive compositions contain inorganic elements with higher EUV absorption than hydrocarbons, ensuring sensitivity even through a non-chemically amplified mechanism. They are also known to be less sensitive to stochastic variations and to produce fewer line edge roughness and defects.

[0007] Inorganic photoresists based on peroxopolyacids of tungsten and tungsten mixed with niobium, titanium, and / or tantalum have been reported for patterning radiation-sensitive materials (Patent Document 1 and Non-Patent Document 1).

[0008] These materials have been effective in patterning large features in a bilayer configuration using deep UV, x-ray, and electron beam sources. More recently, impressive performance has been reported when cationic hafnium metal oxide sulfate (HfSOx) materials with peroxo complexing agents were used to develop 15 nm half-pitch (HP) patterns using projection EUV exposure (Patent Document 2 and Non-Patent Document 2). This system demonstrates the highest performance of non-CA photoresists and has an optical speed approaching the requirements for a viable EUV photoresist. However, hafnium metal oxide sulfate materials with peroxo complexing agents have several practical drawbacks. First, these materials are coated with a highly corrosive sulfuric acid / hydrogen peroxide mixture and have poor storage stability. Second, as a complex mixture, their structure cannot be easily modified to improve performance. Third, they must be developed using extremely high concentrations, such as 25% by weight, of TMAH (tetramethylammonium hydroxide) solution.

[0009] Recently, tin-containing molecules have been actively researched due to their excellent extreme ultraviolet absorption. Organotin polymers, one such polymer, enable negative-tone patterning that is resistant to removal by organic developers through oxo-bond crosslinking with surrounding polymer chains as alkyl ligands dissociate upon light absorption or the secondary electrons generated by the absorption. While these organotin polymers have demonstrated dramatic improvements in sensitivity while maintaining resolution and line edge roughness, further improvements in the patterning properties are required for commercialization. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] U.S. Patent No. 5,061,599 [Patent Document 2] US Patent Application Publication No. 2011 / 0045406 [Non-patent literature]

[0011] [Non-Patent Document 1] H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298-300, 1986 [Non-patent document 2] JKStowers, A.Telecky, M.Kocsis, BLClark, DAKEszler, A.Grenville, CNAnderson, PPNaulleau, Proc.SPIE, 7969, 796915, 2011 Summary of the Invention [Problem to be solved by the invention]

[0012] An object of the present invention is to provide a semiconductor photoresist composition that has excellent coating properties, sensitivity, and pattern formability.

[0013] Another object of the present invention is to provide a pattern forming method using the above semiconductor photoresist composition. [Means for solving the problem]

[0014] The semiconductor photoresist composition according to the present invention comprises an organometallic compound, an additive represented by the following Chemical Formula 1, and a solvent.

[0015] [ka]

[0016] In the above chemical formula 1, R 1is an alkyl group having 1 to 12 carbon atoms substituted with at least one halogen atom, a cycloalkyl group having 3 to 10 carbon atoms substituted with at least one halogen atom, an aryl group having 6 to 20 carbon atoms substituted with at least one halogen atom, a cycloalkyl group having 3 to 10 carbon atoms substituted with a haloalkyl group having 1 to 5 carbon atoms substituted with at least one halogen atom, an aryl group having 6 to 20 carbon atoms substituted with a haloalkyl group having 1 to 5 carbon atoms substituted with at least one halogen atom, or a combination thereof.

[0017] R in the above chemical formula 1 1 may be an alkyl group having 1 to 12 carbon atoms substituted with 1 to 3 halogen atoms, a cycloalkyl group having 3 to 10 carbon atoms substituted with 1 to 3 halogen atoms, an aryl group having 6 to 20 carbon atoms substituted with 1 to 3 halogen atoms, a cycloalkyl group having 3 to 10 carbon atoms substituted with a haloalkyl group having 1 to 5 carbon atoms substituted with 1 to 3 halogen atoms, an aryl group having 6 to 20 carbon atoms substituted with a haloalkyl group having 1 to 5 carbon atoms substituted with 1 to 3 halogen atoms, or a combination thereof.

[0018] R in the above chemical formula 1 1 may be an alkyl group having 1 to 12 carbon atoms substituted with at least one of fluoro (-F) and iodo (-I), a cycloalkyl group having 3 to 10 carbon atoms substituted with at least one of fluoro (-F) and iodo (-I), a cycloalkyl group having 3 to 10 carbon atoms substituted with at least one of a fluoroalkyl group having 1 to 5 carbon atoms and an iodoalkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms substituted with at least one of fluoroalkyl group having 1 to 5 carbon atoms and an iodoalkyl group having 1 to 5 carbon atoms, or a combination thereof.

[0019] R in the above chemical formula 1 1may be an alkyl group having 1 to 4 carbon atoms substituted with at least one of fluoro (-F) and iodo (-I), a cycloalkyl group having 3 to 6 carbon atoms substituted with at least one of fluoro (-F) and iodo (-I), a cycloalkyl group having 3 to 6 carbon atoms substituted with at least one of fluoromethyl and iodomethyl, an aryl group having 6 to 12 carbon atoms substituted with at least one of fluoro (-F) and iodo (-I), an aryl group having 6 to 12 carbon atoms substituted with at least one of fluoromethyl and iodomethyl, or a combination thereof.

[0020] R in the above chemical formula 1 1 may be a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 1,2-difluoroethyl group, a 1,1,2-trifluoroethyl group, a 1,2,2-trifluoroethyl group, an iodomethyl group, a diiodomethyl group, a triiodomethyl group, a 1-iodoethyl group, a 2-iodoethyl group, a 1,1-diiodoethyl group, a 2,2-diiodoethyl group, a 1,2-diiodoethyl group, a 1,1,2-triiodoethyl group, a 1,2,2-triiodoethyl group, a fluoroiodomethyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, an iodophenyl group, a diiodophenyl group, a triiodophenyl group, a fluoromethylphenyl group, a difluoromethylphenyl group, a trifluoromethylphenyl group, an iodomethylphenyl group, a diiodomethylphenyl group, or a triiodomethylphenyl group.

[0021] The additive represented by Chemical Formula 1 above may be at least one compound selected from the group consisting of compounds listed in Group 1 below.

[0022] [ka]

[0023] The additive is preferably contained in an amount of 0.5% by mass to 10% by mass, with the total mass of the organometallic compound and the additive being 100% by mass.

[0024] The organometallic compound may be an organotin compound.

[0025] The organotin compound is a compound having an alkyl group and -SnOR A and -SnOC(=O)R B and In this case, R A 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; R B may be a hydrogen atom, 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.

[0026] The organotin compound is represented by the following chemical formula 2.

[0027] [ka]

[0028] In the above chemical formula 2, R 2 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, and -Ra -OR b (where R a is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, where R b is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; R 3 ~R 5 are each independently -OR c or -OC(=O)R d is selected from In this case, R c each independently represents 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; R d are each independently a hydrogen atom, 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.

[0029] The semiconductor photoresist composition may further include at least one of an organotin compound represented by the following Chemical Formula 3 and an organotin compound represented by the following Chemical Formula 4:

[0030] [ka]

[0031] In the above chemical formula 3, X' each independently represents -OR 6 or -OC(=O)R 7 and In this case, R 6each independently represents 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; R 7 are each independently a hydrogen atom, 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;

[0032] [ka]

[0033] In the above chemical formula 4, X" is independently -OR 8 or -OC(=O)R 9 and In this case, R 8 each independently represents 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; R 9 each independently represents a hydrogen atom, 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; L is a single bond, a substituted or unsubstituted divalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted divalent saturated or unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted divalent unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, -O-, -C(=O)-, or a combination thereof.

[0034] The total of the organotin compound represented by the chemical formula 3 and the organotin compound represented by the chemical formula 4, and the organotin compound represented by the chemical formula 2 are contained in a mass ratio of 1:1 to 1:20.

[0035] The organotin compound represented by the above chemical formula 2 is represented by at least one of the following chemical formulas 5 to 8.

[0036] [ka]

[0037] In the above Chemical Formulas 5 to 8, R 10 ~R 13 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 aliphatic unsaturated organic group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, an ethoxy group, a propoxy group, or a combination thereof; R e , R f , R g , R m , R o , and R peach independently represents 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; R h , R i , R j , R k , R l , and R n are each independently a hydrogen atom, 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.

[0038] The semiconductor photoresist composition may further include other additives such as a surfactant, a crosslinking agent, a leveling agent, or a combination thereof.

[0039] A pattern forming method according to another embodiment of the present invention includes the steps of forming a layer to be etched on a substrate, applying the above-described semiconductor photoresist composition on the layer to be etched to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and etching the layer to be etched using the photoresist pattern as an etching mask.

[0040] The step of forming the photoresist pattern may use light having a wavelength of 5 nm to 150 nm.

[0041] The pattern forming method may further include forming a resist underlayer film between the substrate and the photoresist film.

[0042] The photoresist pattern may have a width of 5 nm to 100 nm. [Effects of the Invention]

[0043] The present invention provides a semiconductor photoresist composition having relatively excellent resolution and sensitivity. By using the semiconductor photoresist composition of the present invention, it is possible to realize a photoresist pattern having excellent limiting resolution and which does not collapse even when the pattern has a high aspect ratio. [Brief explanation of the drawings]

[0044] [Figure 1] 1 is a schematic cross-sectional view illustrating a method for forming a pattern using a semiconductor photoresist composition according to an embodiment of the present invention. [Figure 2] 1 is a schematic cross-sectional view illustrating a method for forming a pattern using a semiconductor photoresist composition according to an embodiment of the present invention. [Figure 3] 1 is a schematic cross-sectional view illustrating a method for forming a pattern using a semiconductor photoresist composition according to an embodiment of the present invention. [Figure 4] 1 is a schematic cross-sectional view illustrating a method for forming a pattern using a semiconductor photoresist composition according to an embodiment of the present invention. [Figure 5] 1 is a schematic cross-sectional view illustrating a method for forming a pattern using a semiconductor photoresist composition according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0045] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, in describing the present invention, descriptions of functions or configurations that are already known will be omitted in order to clarify the gist of the present invention.

[0046] In order to clearly explain the present invention, parts unnecessary for the explanation will be omitted, and the same or similar components will be designated by the same reference numerals throughout the specification. Furthermore, the size and thickness of each component shown in the drawings are arbitrarily shown for the convenience of explanation, and the present invention is not necessarily limited to those shown in the drawings.

[0047] In the drawings, the thicknesses of various layers and regions are exaggerated to clearly show them. Also, in the drawings, the thicknesses of some layers and regions are exaggerated for the convenience of explanation. When a layer, film, region, plate, or other portion is said to be "on" another portion, this includes not only the case where it is "directly on" the other portion, but also the case where there is another portion therebetween.

[0048] In the present invention, "substituted" means that a hydrogen atom is replaced with a deuterium atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, -NRR' (wherein R and R' are each independently a hydrogen atom, 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" (wherein R, R', and R" are each independently a hydrogen atom, "Unsubstituted" means that the hydrogen atoms remain as hydrogen atoms, without being substituted with other substituents.

[0049] As used herein, unless otherwise defined, the term "alkyl group" refers to a straight-chain or branched aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0050] 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, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. For example, the alkyl group having 1 to 4 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. 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, a tert-butyl group, or a 2,2-dimethylpropyl group.

[0051] In the present invention, unless otherwise defined, the term "cycloalkyl group" refers to a monovalent cyclic aliphatic saturated hydrocarbon group.

[0052] 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, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 3 to 5 carbon atoms, or a cycloalkyl group having 3 to 4 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.

[0053] As used herein, the term "aliphatically unsaturated organic group" refers to a hydrocarbon group in which the bonds between carbon atoms in the molecule contain double bonds, triple bonds, or combinations thereof.

[0054] The aliphatic unsaturated organic group may be an aliphatic unsaturated organic group having 2 to 8 carbon atoms. For example, the aliphatic unsaturated organic group may be an aliphatic unsaturated organic group having 2 to 7 carbon atoms, an aliphatic unsaturated organic group having 2 to 6 carbon atoms, an aliphatic unsaturated organic group having 2 to 5 carbon atoms, or an aliphatic unsaturated organic group having 2 to 4 carbon atoms. For example, the aliphatic unsaturated organic group having 2 to 4 carbon atoms may be a vinyl group, an ethynyl group, an allyl group, a 1-propenyl group, a 1-methyl-1-propenyl group, a 2-propenyl group, a 2-methyl-2-propenyl group, a 1-propynyl group, a 1-methyl-1propynyl group, a 2-propynyl group, a 2-methyl-2-propynyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group.

[0055] As used herein, the term "aryl group" refers to a substituent in which all elements of the cyclic substituent have p-orbitals and these p-orbitals form conjugation, and includes monocyclic and fused polycyclic (i.e., rings that share adjacent pairs of carbon atoms) functional groups.

[0056] As used herein, the term "heteroaryl group" refers to 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 can be directly linked by a sigma bond, or, when the heteroaryl group contains two or more rings, the two or more rings can be fused to each other. When the heteroaryl group is included in a fused ring structure, each ring can contain 1 to 3 of the above heteroatoms.

[0057] As used herein, unless otherwise defined, the term "alkenyl group" refers to a straight-chain or branched aliphatic hydrocarbon group and an aliphatic unsaturated alkenyl group containing one or more double bonds.

[0058] As used herein, unless otherwise defined, the term "alkynyl group" refers to a straight-chain or branched aliphatic hydrocarbon group and an aliphatic unsaturated alkynyl group containing one or more triple bonds.

[0059] Hereinafter, a semiconductor photoresist composition according to one embodiment of the present invention will be described.

[0060] A semiconductor photoresist composition according to one embodiment of the present invention includes an organometallic compound, an additive, and a solvent, and the additive is represented by the following Chemical Formula 1:

[0061] [ka]

[0062] In the above chemical formula 1, R 1 is an alkyl group having 1 to 12 carbon atoms substituted with at least one halogen atom, a cycloalkyl group having 3 to 10 carbon atoms substituted with at least one halogen atom, an aryl group having 6 to 20 carbon atoms substituted with at least one halogen atom, a cycloalkyl group having 3 to 10 carbon atoms substituted with a haloalkyl group having 1 to 5 carbon atoms substituted with at least one halogen atom, an aryl group having 6 to 20 carbon atoms substituted with a haloalkyl group having 1 to 5 carbon atoms substituted with at least one halogen atom, or a combination thereof.

[0063] The additive represented by Chemical Formula 1 is a halogen-substituted acid compound that strongly absorbs extreme ultraviolet light, and a semiconductor photoresist composition containing the additive can form a pattern with a small amount of light, thereby improving sensitivity.

[0064] The halogen atom refers to fluoro (-F), chloro (-Cl), bromo (-Br), or iodo (-I).

[0065] The haloalkyl group having 1 to 5 carbon atoms means an alkyl group having 1 to 5 carbon atoms substituted with one or more halogen atoms.

[0066] For example, the above haloalkyl group having 1 to 5 carbon atoms can mean an alkyl group having 1 to 5 carbon atoms substituted with one or more of fluoro (-F), chloro (-Cl), bromo (-Br), and iodo (-I).

[0067] More specifically, the haloalkyl group having 1 to 5 carbon atoms can mean an alkyl group having 1 to 5 carbon atoms substituted with one or more of fluoro (-F) and iodo (-I).

[0068] Most specifically, the haloalkyl group having 1 to 5 carbon atoms may mean an alkyl group having 1 to 5 carbon atoms substituted with 1 to 3 substituents selected from fluoro (-F) and iodo (-I).

[0069] As an example, R in the above chemical formula 1 1 may be an alkyl group having 1 to 12 carbon atoms substituted with 1 to 3 halogen atoms, a cycloalkyl group having 3 to 10 carbon atoms substituted with 1 to 3 halogen atoms, an aryl group having 6 to 20 carbon atoms substituted with 1 to 3 halogen atoms, a cycloalkyl group having 3 to 10 carbon atoms substituted with a haloalkyl group having 1 to 5 carbon atoms substituted with 1 to 3 halogen atoms, an aryl group having 6 to 20 carbon atoms substituted with a haloalkyl group having 1 to 5 carbon atoms substituted with 1 to 3 halogen atoms, or a combination thereof.

[0070] As a specific example, R 1 may be an alkyl group having 1 to 12 carbon atoms substituted with at least one of fluoro (-F) and iodo (-I); a cycloalkyl group having 3 to 10 carbon atoms substituted with at least one of fluoro (-F), iodo (-I), a fluoroalkyl group having 1 to 5 carbon atoms and an iodoalkyl group having 1 to 5 carbon atoms; an aryl group having 6 to 20 carbon atoms substituted with at least one of fluoro (-F), iodo (-I), a fluoroalkyl group having 1 to 5 carbon atoms and an iodoalkyl group having 1 to 5 carbon atoms; or a combination thereof.

[0071] For example, R in the above chemical formula 1 1 may be an alkyl group having 1 to 4 carbon atoms substituted with at least one of fluoro (-F) and iodo (-I); a cycloalkyl group having 3 to 6 carbon atoms substituted with at least one of fluoro (-F), iodo (-I), a fluoromethyl group, and an iodomethyl group; an aryl group having 6 to 12 carbon atoms substituted with at least one of fluoro (-F), iodo (-I), a fluoromethyl group, and an iodomethyl group, or a combination thereof.

[0072] In particular, R in the above chemical formula 1 1 In the case where the alkyl group has three or less carbon atoms, it may be more advantageous since defects that may occur in the pattern after exposure are further reduced.

[0073] That is, R in the above chemical formula 1 1 When R is an alkyl group, it is preferable that R 1 is an alkyl group having 1 to 3 carbon atoms substituted with at least one halogen atom, specifically, R 1 is an alkyl group having 1 to 3 carbon atoms substituted with 1 to 3 halogen atoms, more specifically, R 1 may be an alkyl group having 1 to 3 carbon atoms substituted with at least one of fluoro (-F) and iodo (-I).

[0074] In one embodiment, R in Formula 1 above 1 When R is an alkyl group, it is preferable that R 1 is an alkyl group having 1 to 4 carbon atoms substituted with at least one halogen atom, specifically, R 1 is an alkyl group having 1 to 4 carbon atoms substituted with 1 to 4 halogen atoms, more specifically, R 1 may be an alkyl group having 1 to 4 carbon atoms substituted with at least one of fluoro (-F) and iodo (-I).

[0075] R in the above chemical formula 1 1In the case of alkyl groups with 4 or more carbon atoms, especially 5 or more, non-volatile substances due to increased molecular weight and boiling point may remain for a relatively long time during pattern formation, causing non-uniformity of the coating film, and the remaining substances after exposure may form contaminants such as scum within the pattern, reducing pattern formability.

[0076] In one embodiment, R in Formula 1 above 1 may be a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 1,2-difluoroethyl group, a 1,1,2-trifluoroethyl group, a 1,2,2-trifluoroethyl group, an iodomethyl group, a diiodomethyl group, a triiodomethyl group, a 1-iodoethyl group, a 2-iodoethyl group, a 1,1-diiodoethyl group, a 2,2-diiodoethyl group, a 1,2-diiodoethyl group, a 1,1,2-triiodoethyl group, a 1,2,2-triiodoethyl group, a fluoroiodomethyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, an iodophenyl group, a diiodophenyl group, a triiodophenyl group, a fluoromethylphenyl group, a difluoromethylphenyl group, a trifluoromethylphenyl group, an iodomethylphenyl group, a diiodomethylphenyl group, or a triiodomethylphenyl group.

[0077] In one embodiment, R in Formula 1 above 1 is, for example, a fluorophenyl group, an iodophenyl group, a fluoromethylphenyl group, a difluoromethylphenyl group, a trifluoromethylphenyl group, an iodomethylphenyl group, a diiodomethylphenyl group, or a triiodomethylphenyl group, the compound represented by Chemical Formula 1 is a mono-substituted benzoic acid. The mono-substituted benzoic acid includes compounds in which the substitution position is the 2-position, the 3-position, or the 4-position.

[0078] In one embodiment, R in Formula 1 above 1is, for example, a difluorophenyl group or a diiodophenyl group, the compound represented by Chemical Formula 1 is a disubstituted benzoic acid. The disubstituted benzoic acid includes compounds in which the substitution positions are the 2- and 3-positions, the 2- and 4-positions, the 2- and 5-positions, the 2- and 6-positions, or the 3- and 4-positions.

[0079] In one embodiment, R in Formula 1 above 1 is, for example, a trifluorophenyl group or a triiodophenyl group, the compound represented by Chemical Formula 1 is a trisubstituted benzoic acid. The trisubstituted benzoic acid includes compounds in which the substitution positions are 2-, 3-, and 4-positions; 2-, 3-, and 5-positions; 2-, 3-, and 6-positions; 2-, 4-, and 5-positions; or 2-, 4-, and 6-positions.

[0080] In a specific embodiment, the additive represented by the above Chemical Formula 1 is a compound selected from the group of compounds listed in Group 1 below.

[0081] [ka]

[0082] The additive is preferably contained in an amount of 0.5% by mass to 10% by mass, with the total mass of the organometallic compound and the additive being 100% by mass.

[0083] For example, the additive is contained in an amount of 1.0 mass % to 10 mass %, 2.0 mass % to 8.0 mass %, or 2.0 mass % to 6.0 mass %.

[0084] The semiconductor photoresist composition may contain the additive in an amount of 0.5% by mass to 10% by mass, for example, 1.0% by mass to 10% by mass, for example, 2.0% by mass to 8.0% by mass, for example, 2.0% by mass to 6.0% by mass, where the total mass of the organometallic compound and the additive is 100% by mass. When the additive is contained in the amount described above, the sensitivity and resolution can be further improved.

[0085] In other words, the semiconductor photoresist composition according to the present invention can contain 90% by mass to 99.5% by mass of the organometallic compound and 0.5% by mass to 10% by mass of the additive, where the total mass of the organometallic compound and the additive is 100% by mass; specifically, the composition can contain 92% by mass to 98% by mass of the organometallic compound and 2% by mass to 8% by mass of the additive, or 94% by mass to 98% by mass of the organometallic compound and 2% by mass to 6% by mass of the additive.

[0086] In the organometallic compound, the metal atom strongly absorbs extreme ultraviolet light at 13.5 nm, and organometallic compounds containing this metal atom have excellent sensitivity to high-energy light. As a result, the organometallic compound according to the present invention can exhibit superior stability and sensitivity compared to conventional organic and / or inorganic photoresists.

[0087] The organometallic compound may also be, for example, an organotin compound.

[0088] The organotin compound may contain at least one of an alkyltinoxo group (alkylstannyloxy group) and an alkyltincarboxyl group (alkylstannyloxycarbonyl group).

[0089] The organotin compound is a compound having an alkyl group and -SnOR A and -SnOC(=O)R B and at least one of R A 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; R Bmay be a hydrogen atom, 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.

[0090] As an example, the organotin compound is a compound represented by the following chemical formula 2:

[0091] [ka]

[0092] In the above chemical formula 2, R 2 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, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, and -R a -OR b (where R a is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, and R b is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; R 3 ~R 5 are each independently -OR c or -OC(=O)R d is selected from R c each independently represents 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; R dare each independently a hydrogen atom, 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.

[0093] A semiconductor photoresist composition according to one embodiment of the present invention may further include at least one of an organotin compound represented by the following Chemical Formula 3 and an organotin compound represented by the following Chemical Formula 4, in addition to the organotin compound represented by Chemical Formula 2:

[0094] [ka]

[0095] In the above chemical formula 3, X' each independently represents -OR 6 or -OC(=O)R 7 and In this case, R 6 each independently represents 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; R 7 are each independently a hydrogen atom, 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;

[0096] [ka]

[0097] In the above chemical formula 4, X" is independently -OR 8 or -OC(=O)R 9 and In this case, R 8 each independently represents 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; R 9 each independently represents a hydrogen atom, 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; L is a single bond, a substituted or unsubstituted divalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted divalent saturated or unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted divalent unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, -O-, -C(=O)-, or a combination thereof.

[0098] A semiconductor photoresist composition according to one embodiment of the present invention simultaneously contains an organotin compound and an additive represented by Chemical Formula 1, an organotin compound represented by Chemical Formula 3, and / or an organotin compound represented by Chemical Formula 4, thereby providing a semiconductor photoresist composition having excellent sensitivity and pattern formability.

[0099] By appropriately adjusting the ratio of the organotin compound represented by Chemical Formula 3 or the organotin compound represented by Chemical Formula 4, the degree of ligand dissociation from the copolymer can be controlled, and thereby the degree of cross-linking with peripheral chains through oxo bonds by radicals generated as the ligand dissociates can be controlled, resulting in a semiconductor photoresist with excellent sensitivity and resolution. In other words, by simultaneously containing the organotin compound represented by Chemical Formula 2 and the organotin compound represented by Chemical Formula 3 or the organotin compound represented by Chemical Formula 4, a semiconductor photoresist with excellent coatability, sensitivity, and pattern formability can be provided.

[0100] For example, the total of the organotin compound represented by the chemical formula 3 and the organotin compound represented by the chemical formula 4, and the organotin compound represented by the chemical formula 2 are contained in a mass ratio of 1:1 to 1:20 (the total of the organotin compound represented by the chemical formula 3 and the organotin compound represented by the chemical formula 4:the organotin compound represented by the chemical formula 2), for example, 1:1 to 1:19, for example, 1:1 to 1:18, for example, 1:1 to 1:17, for example, 1:1 to 1: The organotin compound represented by Chemical Formula 2 may be present in a mass ratio of, for example, 1:1 to 1:16, for example, 1:1 to 1:15, for example, 1:1 to 1:14, for example, 1:1 to 1:13, for example, 1:1 to 1:12, for example, 1:1 to 1:11, for example, 1:1 to 1:10, for example, 1:1 to 1:9, for example, 1:1 to 1:8, for example, 1:1 to 1:7, for example, 1:1 to 1:6, for example, 1:1 to 1:5, for example, 1:1 to 1:4, for example, 1:1 to 1:3, or for example, 1:1 to 1:2, but is not limited to these. When the mass ratio of the organotin compound represented by Chemical Formula 2 to the organotin compound represented by Chemical Formula 3, the organotin compound represented by Chemical Formula 4, or a combination thereof satisfies the above range, a semiconductor photoresist composition having excellent sensitivity and resolution can be provided.

[0101] R of the compound represented by the above chemical formula 2 2may be a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 8 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a combination thereof, such as a hydrogen atom, 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, or a combination thereof.

[0102] The organotin compound represented by the above chemical formula 2 is preferably at least one of the compounds represented by the following chemical formulas 5 to 8.

[0103] [ka]

[0104] In the above Chemical Formulas 5 to 8, R 10 ~R 13 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 aliphatic unsaturated organic group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, an ethoxy group, a propoxy group, or a combination thereof; R e , R f , R g , R m , R o , and R peach independently represents 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; R h , R i , R j , R k , R l , and R n are each independently a hydrogen atom, 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.

[0105] In a semiconductor photoresist composition according to one embodiment of the present invention, the organotin compound represented by Chemical Formula 2 may be contained in an amount of, but is not limited to, 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, or for example, 1% to 5% by weight, based on 100% by weight of the semiconductor photoresist composition. When the organotin compound represented by Chemical Formula 2 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.

[0106] The compound represented by the above chemical formula 1, the organotin compound represented by the above chemical formula 2, and the organotin compounds represented by chemical formulas 3 and 4 can be synthesized by appropriately referring to conventionally known synthesis methods. More specifically, those skilled in the art can easily synthesize them by referring to the synthesis methods described in the Examples.

[0107] The solvent contained in the semiconductor resist composition according to one embodiment of the present invention may be an organic solvent, and examples thereof include, but are not limited to, aromatic compounds (e.g., xylene, toluene, etc.), alcohols (e.g., 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropyl alcohol, 1-propanol, etc.), ethers (e.g., anisole, tetrahydrofuran, etc.), esters (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, etc.), ketones (e.g., methyl ethyl ketone, 2-heptanone, etc.), and mixtures thereof.

[0108] In one embodiment of the present invention, the semiconductor resist composition may further include a resin in addition to the organotin compound, the additive represented by Chemical Formula 1, and a solvent.

[0109] The resin may be a phenolic resin containing at least one aromatic moiety listed in Group 2 below.

[0110] [ka]

[0111] The resin may have a weight-average molecular weight of 500 to 20,000. The weight-average molecular weight of the resin can be measured by gel permeation chromatography (GPC).

[0112] The resin may be contained in an amount of 0.1% by mass to 50% by mass relative to the total mass of the semiconductor resist composition.

[0113] When the resin is contained within the above content range, excellent etching resistance and heat resistance can be obtained.

[0114] Furthermore, a semiconductor resist composition according to one embodiment of the present invention preferably comprises the organotin compound described above, an additive represented by Chemical Formula 1, a solvent, and a resin. However, the semiconductor resist composition according to the above embodiment may further contain other additives in some cases. Examples of the other additives include a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, or a combination thereof.

[0115] The surfactant may be, for example, but not limited to, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, or a combination thereof.

[0116] 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, and polymer-based crosslinking agents. Examples of crosslinking agents having at least two crosslink-forming substituents that can be used include methoxymethylated glycoluril, butoxymethylated glycoluril, 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-cyclohexanedicarboxylate, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, and methoxymethylated thiourea.

[0117] The leveling agent is used to improve the coating flatness during printing, and any known leveling agent that is commercially available can be used.

[0118] The organic acid may be, but is 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.

[0119] The quencher may be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0120] The amounts of these other additives used can be easily adjusted depending on the desired physical properties, and they may not be added at all.

[0121] Furthermore, the semiconductor resist composition may further contain a silane coupling agent as an adhesion improver to improve adhesion to the substrate (e.g., to improve adhesion of the semiconductor resist composition to the substrate). Examples of silane coupling agents include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; or silane compounds containing carbon-carbon unsaturated bonds, such as 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; and trimethoxy[3-(phenylamino)propyl]silane.

[0122] The semiconductor photoresist composition does not cause or hardly causes pattern collapse even when forming a pattern with a high aspect ratio. Therefore, to form a fine pattern having a width of, for example, 5 nm to 100 nm, for example, a fine pattern having a width of 5 nm to 80 nm, for example, a fine pattern having a width of 5 nm to 70 nm, for example, a fine pattern having a width of 5 nm to 50 nm, for example, a fine pattern having a width of 5 nm to 40 nm, for example, a fine pattern having a width of 5 nm to 30 nm, for example, a fine pattern having a width of 5 nm to 20 nm, or for example, a fine pattern having a width of 5 nm to 10 nm, the composition can be used in a photoresist process using light with a wavelength of 5 nm to 150 nm, for example, a photoresist process using light with a wavelength of 5 nm to 100 nm, for example, a photoresist process using light with a wavelength of 5 nm to 80 nm, for example, a photoresist process using light with a wavelength of 5 nm to 50 nm, for example, a photoresist process using light with a wavelength of 5 nm to 30 nm, or for example, a photoresist process using light with a wavelength of 5 nm to 20 nm. Therefore, by using the semiconductor photoresist composition according to one embodiment of the present invention, extreme ultraviolet lithography using an EUV light source with a wavelength of 13.5 nm can be realized.

[0123] According to another embodiment of the present invention, there is provided a method for forming a pattern using the above-described semiconductor photoresist composition. For example, the pattern formed may be a photoresist pattern.

[0124] A method for forming a pattern according to an embodiment of the present invention includes the steps of forming a layer to be etched on a substrate, applying the above-described semiconductor photoresist composition on the layer to be etched to form a photoresist layer, patterning the photoresist layer to form a photoresist pattern, and etching the layer to be etched using the photoresist pattern as an etching mask.

[0125] A method for forming a pattern using the above-described semiconductor photoresist composition will be described below with reference to Figures 1 to 5. Figures 1 to 5 are schematic cross-sectional views illustrating the pattern formation method using the semiconductor photoresist composition according to the present invention.

[0126] Referring to FIG. 1, first, an object to be etched is provided. An example of the object to be etched may be a thin film 102 formed on a semiconductor substrate 100. The following description will be limited to the case where the object to be etched is the thin film 102. The surface of the thin film 102 is cleaned to remove 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.

[0127] Next, a composition for forming a resist underlayer film to form a resist underlayer film 104 is coated on the surface of the cleaned thin film 102 by spin coating. However, the present invention is not 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.

[0128] Although the step of coating the resist underlayer film can be omitted, the case of coating the resist underlayer film will be described below.

[0129] Thereafter, drying and baking steps are performed to form a resist underlayer film 104 on the thin film 102. The baking process can be performed at 100 to 500°C, for example, 100 to 300°C.

[0130] The resist underlayer film 104 is formed between the substrate 100 and the photoresist film 106, and can prevent unevenness in the photoresist line width and interference with pattern formability when radiation reflected from the interface between the substrate 100 and the photoresist film 106 or from the interlayer hard mask is scattered into unintended photoresist regions.

[0131] 2, the above-described semiconductor photoresist composition is coated on the resist underlayer film 104 to form a photoresist film 106. The photoresist film 106 may be formed by coating the above-described semiconductor photoresist composition on a thin film 102 formed on a substrate 100 and then curing the composition through a heat treatment process.

[0132] More specifically, the step of forming a pattern using the semiconductor photoresist composition may include a step of applying the above-described semiconductor photoresist composition onto the substrate 100 on which the thin film 102 has been formed by a method such as spin coating, slit coating, or inkjet printing, and a step of drying the applied semiconductor photoresist composition to form a photoresist film 106.

[0133] The semiconductor photoresist composition has already been described in detail, so a duplicated description will be omitted.

[0134] Next, a first baking step is performed to heat the substrate 100 on which the photoresist film 106 is formed. The first baking step can be performed at a temperature of 80°C to 120°C.

[0135] Referring to FIG. 3, the photoresist film 106 is selectively exposed to light.

[0136] As an example, examples of light that can be used in the above exposure process include light with short wavelengths such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), as well as light with high-energy wavelengths such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0137] More specifically, the exposure light according to one embodiment of the present invention may be short wavelength light having a wavelength range of 5 nm to 150 nm, or may be light having a high energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0138] The exposed regions 106a in the photoresist film 106 form polymers through crosslinking reactions such as condensation between organometallic compounds, and therefore have a different solubility from the regions left unexposed by the photomask 110, i.e., the unexposed regions 106b of the photoresist film 106.

[0139] Next, a second baking step is performed on the substrate 100. The second baking step can be performed at a temperature of 90° C. to 200° C. By performing the second baking step, the exposed region 106a of the photoresist film 106 becomes less soluble in a developer.

[0140] 4 shows a photoresist pattern 108 formed by dissolving and removing the photoresist film 106b corresponding to the unexposed region using a developer. Specifically, the photoresist film 106b corresponding to the unexposed region is dissolved using an organic solvent such as 2-heptanone and then removed, thereby completing the photoresist pattern 108 corresponding to a negative tone image.

[0141] As described above, the developer used in the pattern formation method according to one embodiment of the present invention may be an organic solvent. Examples of the organic solvent used in the pattern formation method according to one embodiment of the present invention 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 γ-butyrolactone, aromatic compounds such as benzene, xylene, and toluene, and combinations thereof.

[0142] However, the photoresist pattern according to an embodiment of the present invention is not necessarily limited to being formed as a negative tone image, but may be formed as a positive tone image. In this case, developers that can be used to form a positive tone image include quaternary ammonium hydroxides such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof.

[0143] As described above, the photoresist pattern 108 formed by exposure to 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. As an example, the photoresist pattern 108 is formed to have a width 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, or 5 nm to 10 nm.

[0144] On the other hand, the photoresist pattern 108 can have a pitch with a half pitch of 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 line width roughness of 10 nm or less, 5 nm or less, 3 nm or less, 2 nm or less, 1 nm or less.

[0145] Next, the resist underlayer film 104 is etched using the photoresist pattern 108 as an etching mask. This etching process forms an organic film pattern 112. The formed organic film pattern 112 may also have a width corresponding to the photoresist pattern 108.

[0146] 5, the photoresist pattern 108 is used as an etching mask to etch the exposed thin film 102. As a result, the thin film 102 is formed into a thin film pattern 114.

[0147] The thin film 102 can be etched by dry etching using an etching gas, such as CHF3, CF4, Cl2, BCl3, or a mixture thereof.

[0148] The thin film pattern 114 formed using the photoresist pattern 108 formed in the exposure process performed using an EUV light source may have a width corresponding to the photoresist pattern 108. For example, it may have a width of 5 nm to 100 nm, similar to the photoresist pattern 108. For example, the thin film pattern 114 formed by the exposure process performed using an EUV light source may have a width 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, or 5 nm to 20 nm, similar to the photoresist pattern 108, and more specifically, it is formed to a width of 20 nm or less. [Example]

[0149] The present invention will be described in more detail below with reference to examples of preparing the above-mentioned semiconductor photoresist composition, but the technical features of the present invention are not limited to these examples.

[0150] (Synthesis of organotin compounds) (Synthesis Example 1) 20 g (51.9 mmol) of Ph3SnCl was dissolved in 70 mL of THF in a 250 mL two-necked round-bottom flask and cooled to 0 °C in an ice bath. Then, butylmagnesium chloride (BuMgCl) 1 M THF solution (62.3 mmol) was slowly added dropwise. After the addition was completed, the mixture was stirred at 25 °C for 12 hours to obtain the compound represented by the following chemical formula 9a.

[0151] Then, the compound of formula 9a (10 g, 24.6 mmol) was dissolved in 50 mL of CHCl, and 3 equivalents of a 2 M HCl diethyl ether solution (73.7 mmol) was slowly added dropwise over 30 minutes at -78°C. After stirring at 25°C for 12 hours, the solvent was concentrated and distilled under vacuum to obtain the compound represented by formula 9b below.

[0152] After that, 25 mL of acetic acid was slowly added dropwise to 10 g (25.6 mmol) of the compound of formula 9b at 25°C, and the mixture was heated under reflux for 12 hours. After the temperature was lowered to 25°C, the acetic acid was distilled off under vacuum to finally obtain the compound represented by the following formula 9.

[0153] [ka]

[0154] (Production of semiconductor photoresist composition) (Examples 1 to 4 and Comparative Examples 1 to 5) According to the compositions shown in Table 1 below, the compound represented by Chemical Formula 9 obtained in Synthesis Example 1 and each additive were dissolved in propylene glycol methyl ether acetate to a solid content of 3 mass %, and the solution was filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to produce semiconductor photoresist compositions. The numbers in parentheses in Table 1 below indicate the content relative to the total mass of the organotin compound and additives.

[0155] (Photoresist film formation) Circular silicon wafers with a diameter of 4 inches and having a native oxide film surface were used as substrates for thin film deposition. Prior to thin film deposition, the wafers were treated in a UV ozone cleaning system for 10 minutes. The semiconductor photoresist compositions of Examples 1 to 4 and Comparative Examples 1 to 5 were spin-coated onto the treated substrates at 1500 rpm for 30 seconds and baked at 110°C for 60 seconds (post-apply bake, PAB) to form thin films.

[0156] The thickness of the coated and baked film was then measured by ellipsometry to be 25 nm.

[0157] [Table 1]

[0158] (Evaluation 1: Coatability) The surface roughness (Rq value) of the photoresist films produced by the above coating method in Examples 1 to 4 and Comparative Examples 1 to 5 was measured using atomic force microscopy (AFM), and the results are shown in Table 2 below.

[0159] (Rating 2: Sensitivity) EUV light was projected onto wafers coated with the photoresist compositions of Examples 1 to 4 and Comparative Examples 1 to 5 at varying exposure doses using a micro-area exposure tool (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET).

[0160] The resist and substrate were then post-exposure baked (PEB) on a hotplate at 160°C for 120 seconds. The baked film was then immersed in a developer (2-heptanone) for 30 seconds each, followed by a 10-second wash in the same developer to form a negative-tone image, i.e., remove the unexposed coating. A final hotplate bake at 150°C for 2 minutes yielded a 1:1 L / S pattern.

[0161] The Eop value that allows a pattern with a desired line width (14 nm) to be formed from the L / S pattern was measured using a field emission scanning electron microscope (FE-SEM), and the values ​​are shown in Table 2 below.

[0162] [Table 2]

[0163] As is clear from the results in Table 2 above, the semiconductor photoresist compositions of Examples 1 to 4 have better coating properties and sensitivity than Comparative Example 1, which does not contain any additive, and the semiconductor photoresist compositions of Comparative Examples 2 to 5, which contain additives not included in Chemical Formula 1 of the present application.

[0164] Although specific embodiments of the present invention have been described and illustrated above, it will be apparent to those skilled in the art that the present invention is not limited to the described embodiments, and that various modifications and variations are possible without departing from the spirit and scope of the present invention. Therefore, such modifications and variations should not be understood separately from the technical spirit and perspective of the present invention, and the modified embodiments should be included within the scope of the claims of the present invention. [Explanation of symbols]

[0165] 100 boards 102 Thin Film 104 Resist underlayer film 106 Photoresist film 106a Exposed area 106b Unexposed area 108 Photoresist pattern 112 Organic film pattern 110 Patterned hard mask 114 Thin Film Pattern

Claims

1. Organometallic compounds; An additive represented by the following chemical formula 1: solvent Including, the organometallic compound is an organotin compound, The organotin compound is a compound represented by the following Chemical Formula 2: 【Transformation 3】 In the above Chemical Formula 2, R 2 is selected from 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, and -R a -O-R b (wherein R a is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, and R b is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms); R 3 to R 5 are each independently selected from —OR c or —OC(═O)R d ; In this case, each R c is 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, or a combination thereof; Each R d is independently a hydrogen atom, 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: 【Chemistry 1】 In the above Chemical Formula 1, R １ is an alkyl group having 1 to 12 carbon atoms substituted with at least one halogen atom, a cycloalkyl group having 3 to 10 carbon atoms substituted with at least one halogen atom, an aryl group having 6 to 20 carbon atoms substituted with at least one halogen atom, a cycloalkyl group having 3 to 10 carbon atoms substituted with a haloalkyl group having 1 to 5 carbon atoms substituted with at least one halogen atom, an aryl group having 6 to 20 carbon atoms substituted with a haloalkyl group having 1 to 5 carbon atoms substituted with at least one halogen atom, or a combination thereof.

2. R in Formula 1 １ is an alkyl group having 1 to 12 carbon atoms substituted with 1 to 3 halogen atoms, a cycloalkyl group having 3 to 10 carbon atoms substituted with 1 to 3 halogen atoms, an aryl group having 6 to 20 carbon atoms substituted with 1 to 3 halogen atoms, a cycloalkyl group having 3 to 10 carbon atoms substituted with a haloalkyl group having 1 to 5 carbon atoms substituted with 1 to 3 halogen atoms, an aryl group having 6 to 20 carbon atoms substituted with a haloalkyl group having 1 to 5 carbon atoms substituted with 1 to 3 halogen atoms, or a combination thereof.

3. R in Formula 1 １ is an alkyl group having 1 to 12 carbon atoms substituted with at least one of fluoro (-F) and iodine (-I), a cycloalkyl group having 3 to 10 carbon atoms substituted with at least one of fluoro (-F) and iodine (-I), a cycloalkyl group having 3 to 10 carbon atoms substituted with at least one of a fluoroalkyl group having 1 to 5 carbon atoms and an iodoalkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms substituted with at least one of fluoro (-F) and iodine (-I), an aryl group having 6 to 20 carbon atoms substituted with at least one of a fluoroalkyl group having 1 to 5 carbon atoms and an iodoalkyl group having 1 to 5 carbon atoms, or a combination thereof.

4. R in Formula 1 １ is an alkyl group having 1 to 4 carbon atoms substituted with at least one of fluoro (-F) and iodine (-I), a cycloalkyl group having 3 to 6 carbon atoms substituted with at least one of fluoro (-F) and iodine (-I), a cycloalkyl group having 3 to 6 carbon atoms substituted with at least one of a fluoromethyl group and an iodomethyl group, an aryl group having 6 to 12 carbon atoms substituted with at least one of fluoro (-F) and iodine (-I), an aryl group having 6 to 12 carbon atoms substituted with at least one of a fluoromethyl group and an iodomethyl group, or a combination thereof.

5. R in Formula 1 １ means a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 1,2-difluoroethyl group, a 1,1,2-trifluoroethyl group, a 1,2,2-trifluoroethyl group, an iodomethyl group, a diiodomethyl group, a triiodomethyl group, a 1-iodoethyl group, a 2-iodoethyl group, a 1,1-diiodoethyl group, a 2,2-diiodoethyl group, a 1,2-diiodoethyl group, 2. The semiconductor photoresist composition according to claim 1, wherein the iodomethyl group is a 1,1,2-triiodoethyl group, a 1,2,2-triiodoethyl group, a fluoroiodomethyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, an iodophenyl group, a diiodophenyl group, a triiodophenyl group, a fluoromethylphenyl group, a difluoromethylphenyl group, a trifluoromethylphenyl group, an iodomethylphenyl group, a diiodomethylphenyl group, or a triiodomethylphenyl group.

6. 2. The composition for semiconductor photoresist according to claim 1, wherein the additive represented by Chemical Formula 1 is at least one compound selected from the group consisting of compounds listed in Group 1 below: 【Chemistry 2】

7. 2. The semiconductor photoresist composition according to claim 1, wherein the additive is contained in an amount of 0.5% by mass to 10% by mass, with the total mass of the organometallic compound and the additive being 100% by mass.

8. 2. The semiconductor photoresist composition according to claim 1, further comprising at least one of an organotin compound represented by the following Chemical Formula 3 and an organotin compound represented by the following Chemical Formula 4: 【Chemistry 4】 In the above Chemical Formula 3, Each X' is independently -OR ６ or -OC(=O)R ７ and At this time, R ６ each independently represents 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; R ７ are each independently a hydrogen atom, 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; 【Transformation 5】 In the above Chemical Formula 4, Each X" is independently -OR ８ or -OC(=O)R ９ and At this time, R ８ each independently represents 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; R ９ each independently represents a hydrogen atom, 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; L is a single bond, a substituted or unsubstituted divalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted divalent saturated or unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted divalent unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, -O-, -C(=O)-, or a combination thereof.

9. 2. The semiconductor photoresist composition according to claim 1, wherein the total of the organotin compound represented by Chemical Formula 3 and the organotin compound represented by Chemical Formula 4 and the organotin compound represented by Chemical Formula 2 are contained in a mass ratio of 1:1 to 1:

20.

10. The composition for semiconductor photoresist according to claim 1, wherein the organotin compound represented by Chemical Formula 2 is at least one of compounds represented by the following Chemical Formulas 5 to 8: 【Transformation 6】 In Chemical Formula 5 to Chemical Formula 8, R １０ ~R １３ 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 aliphatic unsaturated organic group having 2 to 20 carbon atoms and containing one or more double or triple bonds, a substituted or unsubstituted aliphatic unsaturated organic group having 2 to 20 carbon atoms, or an unsubstituted aryl group having 6 to 30 carbon atoms, an ethoxy group, a propoxy group, or a combination thereof; R ｅ , R ｆ , R ｇ , R ｍ , R ｏ , and R ｐ each independently represents 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; R ｈ , R ｉ , R ｊ , R ｋ , R ｌ , and R ｎ are each independently a hydrogen atom, 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.

11. 10. The semiconductor photoresist composition of claim 1, further comprising other additives such as a surfactant, a crosslinking agent, a leveling agent, or a combination thereof.

12. forming a film to be etched on a substrate; forming a photoresist film by applying the semiconductor photoresist composition according to any one of claims 1 to 11 onto the film to be etched; patterning the photoresist film to form a photoresist pattern; and The pattern forming method includes etching the target layer using the photoresist pattern as an etching mask.

13. 13. The method of claim 12, wherein the forming of the photoresist pattern uses light having a wavelength of 5 nm to 150 nm.

14. The pattern formation method according to claim 12, further comprising forming a resist underlayer film between the substrate and the photoresist film.

15. 13. The pattern forming method according to claim 12, wherein the photoresist pattern has a width of 5 nm to 100 nm.

Images