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

Abstract

To provide a semiconductor photoresist composition that offers improved developability and stability against moisture, and a method of forming patterns using the same.SOLUTION: A semiconductor photoresist composition according to the present invention includes an organotin compound 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 formation method using the same. [Background technology]

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

[0003] The realization of extreme ultraviolet (EUV) lithography requires the development of compatible photoresists that can achieve a spatial resolution of 16 nm or less. Currently, traditional chemically amplified photoresists are being researched to meet the specifications for resolution, light speed, and 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 long-known fact in electron beam lithography. Chemically amplified (CA) photoresists are designed for high sensitivity, but their typical elemental composition reduces the absorbance of the photoresist at a wavelength of 13.5 nm, resulting in reduced sensitivity, which can be even more problematic under EUV exposure.

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

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

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

[0008] These materials have been effective in patterning large features in bilayer configurations using deep UV, X-ray, and electron beam sources. More recently, projection EUV lithography has shown impressive performance when using cationic hafnium metal oxide sulfide (HfSOx) materials with peroxo-complexing agents to image 15 nm half-pitch (HP) (Patent Document 2 and Non-Patent Document 2). This system exhibits the best performance of non-CA photoresists and has a light speed close to the requirements for a viable EUV photoresist. However, hafnium metal oxide sulfide materials with peroxo-complexing agents have several practical drawbacks. Firstly, the material is coated with a highly corrosive sulfuric acid / hydrogen peroxide mixture and has poor storage stability. Secondly, as a composite mixture, structural modifications for performance improvement are not easy. Thirdly, it must be developed with extremely high concentrations of TMAH (tetramethylammonium hydroxide) solution, such as 25% by mass.

[0009] Recently, tin-containing molecules have been actively researched as they have become known to have excellent absorption of extreme ultraviolet light. In the case of organotin polymers, one such example, the alkyl ligand dissociates due to light absorption or the secondary electrons generated by it, and negative tone patterning that is not removed by organic developers is possible through crosslinking via oxo bonds with surrounding chains. Such organotin polymers have shown a dramatic improvement in sensitivity while maintaining resolution and line edge roughness, but further improvements in patterning properties are needed for commercialization. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] U.S. Patent No. 5061599 [Patent Document 2] U.S. 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] J. K. Stowers, A. Telecky, M. Kocsis, B. L. Clark, D. A. Keszler, A. Grenville, C. N. Anderson, P. P. Naulleau, Proc. SPIE, 7969, 796915, 2011 [Summary of the Invention] [Problems to be Solved by the Invention]

[0012] An object of the present invention is to provide a composition for a semiconductor photoresist having improved developability and stability against moisture.

[0013] Another object of the present invention is to provide a patterning method using the above composition for a semiconductor photoresist. [Means for Solving the Problems]

[0014] The composition for a semiconductor photoresist according to one embodiment of the present invention contains an organotin compound represented by the following Chemical Formula 1 and a solvent.

[0015] [Chemical Formula]

[0016] In the above Chemical Formula 1, R 1 ~R 6Each of these is independently a hydrogen atom, a halogen 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 C3-C20 cycloalkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof. R 7 These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C3-C20 cycloalkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C3-C20 cycloalkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof.

[0017] R in the above chemical formula 1 7 This may be a substituted alkyl group having 1 to 20 carbon atoms.

[0018] R in the above chemical formula 1 1 ~R 6 Each of these may independently be a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl 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.

[0019] R in the above chemical formula 1 1 ~R 6may each independently be a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an iso-propyl group, an iso-butyl group, an iso-pentyl group, an iso-hexyl group, an iso-heptyl group, an iso-octyl group, an iso-nonyl group, an iso-decyl group, a sec-butyl group, a sec-pentyl group, a sec-hexyl group, a sec-heptyl group, a sec-octyl group, a tert-butyl group, a tert-pentyl group, a tert-hexyl group, a tert-heptyl group, a tert-octyl group, a tert-nonyl group, or a tert-decyl group.

[0020] R in Chemical Formula 1 above 1 ~R 6 At least one of them may be a substituted or unsubstituted alkyl group having 1 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.

[0021] R in Chemical Formula 1 above 1 and R 2 At least one of them, R in Chemical Formula 1 above 3 and R 4 At least one of them, and R in Chemical Formula 1 above 5 and R 6 At least one of them may be a substituted or unsubstituted alkyl group having 1 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.

[0022] The above organotin compound may be at least one selected from the group consisting of the compounds listed in Group 1 below.

[0023]

Chemical Formula

[0024] [ka]

[0025] Based on 100% by mass of the total mass of the above semiconductor photoresist composition, the content of the organotin compound may be 1% to 30% by mass.

[0026] The above semiconductor photoresist composition may further contain additives such as surfactants, crosslinking agents, leveling agents, or combinations thereof.

[0027] A pattern formation method according to another embodiment of the present invention includes the steps of: preparing a film to be etched on a substrate; applying the above-mentioned semiconductor photoresist composition on the film to be etched to form a photoresist film; patterning the photoresist film to form a photoresist pattern; and etching the film to be etched using the photoresist pattern as an etching mask.

[0028] The step of forming the above photoresist pattern can use light with a wavelength of 5 nm to 150 nm.

[0029] The above pattern formation method may further include the step of forming a resist underlayer film between the substrate and the photoresist film.

[0030] The above photoresist pattern can have a width of 5 nm to 100 nm. [Effects of the Invention]

[0031] According to the present invention, a semiconductor photoresist composition with improved developability and moisture stability can be provided. [Brief explanation of the drawing]

[0032] [Figure 1] This is a schematic cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment of the present invention. [Figure 2] This is a schematic cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment of the present invention. [Figure 3] This is a schematic cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment of the present invention. [Figure 4] This is a schematic cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment of the present invention. [Figure 5] This is a schematic cross-sectional view illustrating a pattern formation method using a semiconductor photoresist composition according to one embodiment of the present invention. [Modes for carrying out the invention]

[0033] Embodiments of the present invention will be described in detail below with reference to the attached drawings. However, in this description of the present invention, descriptions of functions or configurations that have already been publicly disclosed will be omitted in order to clarify the gist of the present invention.

[0034] To clearly explain the present invention, unnecessary explanatory parts have been omitted, and the same or similar components are given the same reference numerals throughout the specification. Furthermore, the dimensions and thicknesses of each component shown in the drawings are shown arbitrarily for the sake of explanation, and the present invention is not necessarily limited to what is shown.

[0035] In the drawings, thicknesses are shown enlarged to clearly represent various layers and regions. Furthermore, for explanatory purposes, the thicknesses of some layers and regions are exaggerated in the drawings. When a layer, film, region, plate, or other part is said to be "on top of" or "on" another part, this includes not only cases where it is "directly on top of" another part, but also cases where there is another part in between.

[0036] In this specification, "substituted" means that the hydrogen atom is a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, -NRR' (where R and R' are, 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'' (where R, R', and R'' are, independently, a hydrogen atom) This means that the group is substituted with a C1-C30 saturated or unsaturated aliphatic hydrocarbon group, a C3-C30 saturated or unsaturated alicyclic hydrocarbon group, or a C6-C30 aromatic hydrocarbon group, an C1-C30 alkyl group, a C1-C10 haloalkyl group, a C1-C10 alkylsilyl group, a C3-C30 cycloalkyl group, an C6-C30 aryl group, a C1-C20 alkoxy group, or a combination thereof. "Unsubstituted" means that the hydrogen atom remains as a hydrogen atom without being replaced by another substituent.

[0037] In this specification, "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.

[0038] The alkyl group described above 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, 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 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.

[0039] In this specification, "cycloalkyl group" means a monovalent alicyclic saturated hydrocarbon group unless otherwise defined.

[0040] 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, 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 a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and is not limited to these.

[0041] 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 polycyclic (i.e., rings sharing adjacent pairs of carbon atoms) functional groups.

[0042] In this specification, "alkenyl group" means a linear or branched aliphatic hydrocarbon group containing one or more double bonds, which is an aliphatic unsaturated alkenyl group.

[0043] In this specification, unless otherwise defined, "alkynyl group" means a linear or branched aliphatic hydrocarbon group containing one or more triple bonds, specifically an aliphatic unsaturated alkynyl group.

[0044] In the chemical formulas described herein, t-Bu represents a tert-butyl group.

[0045] The following describes a semiconductor photoresist composition according to one embodiment of the present invention.

[0046] A semiconductor photoresist composition according to one embodiment of the present invention comprises an organotin compound represented by the following chemical formula 1 and a solvent.

[0047] [ka]

[0048] In the above chemical formula 1, R1 ~R 6 Each of these is independently a hydrogen atom, a halogen 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 C3-C20 cycloalkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof. R 7 These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C3-C20 cycloalkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C3-C20 cycloalkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof.

[0049] The above organotin compounds have additional coordination sites derived from the -OH group in addition to the oxygen directly bonded to Sn, thus inducing not only intramolecular but also intermolecular coordination bonds, which is advantageous for amorphous matrix formation.

[0050] In particular, compared to the form with a coordination number of 4, the additional coordination bond satisfies the coordination number of Sn, resulting in a form where the Sn atoms are structurally covered, thus improving stability against moisture. This effectively reduces defects due to standing time during the coating process and can also affect the overall coating stability.

[0051] Furthermore, compared to the single-molecule form, strengthening of intermolecular or intramolecular bonds improves adhesion to the substrate and enhances the stability of the thin film.

[0052] Furthermore, by preventing aggregation due to nucleation, the material can be coated in an amorphous state without the use of additives during spin coating, thereby improving sensitivity and coating performance.

[0053] As an example, R in the above chemical formula 1 7 This may be a substituted linear alkyl group having 1 to 20 carbon atoms.

[0054] For example, R in the above chemical formula 1 7 R in the above chemical formula 1 may be an iso-propyl group, iso-butyl group, iso-pentyl group, iso-hexyl group, iso-heptyl group, iso-octyl group, iso-nonyl group, iso-decyl group, sec-butyl group, sec-pentyl group, sec-hexyl group, sec-heptyl group, sec-octyl group, tert-butyl group, tert-pentyl group, tert-hexyl group, tert-heptyl group, tert-octyl group, tert-nonyl group, or tert-decyl group. 7 This may be a benzyl group (a methyl group substituted with a phenyl group).

[0055] As a specific example, R in chemical formula 1 above 7 This may be a substituted or unsubstituted branched alkyl group having 3 to 20 carbon atoms. A branched alkyl group means a form in which the carbon atoms bonded to the metal are secondary, tertiary, or quaternary carbon atoms, and may be, for example, iso-propyl group, iso-butyl group, iso-pentyl group, iso-hexyl group, iso-heptyl group, iso-octyl group, iso-nonyl group, iso-decyl group, sec-butyl group, sec-pentyl group, sec-hexyl group, sec-heptyl group, sec-octyl group, tert-butyl group, tert-pentyl group, tert-hexyl group, tert-heptyl group, tert-octyl group, tert-nonyl group, or tert-decyl group.

[0056] As an example, R in the above chemical formula 1 1 ~R 6Each of these may independently be a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl 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.

[0057] As a specific example, R in chemical formula 1 above 1 ~R 6 Each of these may independently be a hydrogen atom, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an iso-propyl group, an iso-butyl group, an iso-pentyl group, an iso-hexyl group, an iso-heptyl group, an iso-octyl group, an iso-nonyl group, an iso-decyl group, an sec-butyl group, an sec-pentyl group, an sec-hexyl group, an sec-heptyl group, an sec-octyl group, an sec-nonyl group, or an sec-decyl group.

[0058] For example, R in the above chemical formula 1 1 ~R 6 At least one of these may be a substituted or unsubstituted C1-C20 alkyl 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.

[0059] For example, R in the above chemical formula 1 1 and R 2 At least one of the R in the above chemical formula 1 3 and R 4 At least one of the above, and R in chemical formula 1 5 and R 6At least one of these may be a substituted or unsubstituted C1-C20 alkyl 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.

[0060] More specific examples of the organotin compounds mentioned above include the compounds listed in Group 1 below.

[0061] [ka]

[0062] [ka]

[0063] The above organotin compounds strongly absorb extreme ultraviolet light at a wavelength of 13.5 nm and exhibit excellent sensitivity to high-energy light.

[0064] In a semiconductor photoresist composition according to one embodiment of the present invention, the organotin compound may be included in an amount of 1% to 30% by mass, for example, 1% to 25% by mass, for example, 1% to 20% by mass, for example, 1% to 15% by mass, for example, 1% to 10% by mass, for example, 1% to 5% by mass, based on 100% by mass of the total mass of the semiconductor photoresist composition, and is not limited to these amounts. When the organotin compound is included 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.

[0065] A semiconductor photoresist composition according to one embodiment of the present invention, by containing the above-mentioned organotin compound, can become a semiconductor photoresist composition having excellent sensitivity and pattern-forming properties.

[0066] The organotin compounds described above 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.

[0067] The solvent contained in the semiconductor resist composition according to one embodiment of the present invention may be an organic solvent. Examples of organic solvents 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.

[0068] In one embodiment of the present invention, the semiconductor resist composition may further contain a resin in addition to the organotin compound and the solvent.

[0069] The above resin may be a phenolic resin containing at least one aromatic molecule listed in Group 2 below.

[0070] [ka]

[0071] The above 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).

[0072] The above resin may be included in an amount of 0.1% to 50% by mass relative to the total mass of the semiconductor resist composition.

[0073] When the above resin is included within the above-mentioned content range, it can have excellent etching resistance and heat resistance.

[0074] A semiconductor resist composition according to one embodiment of the present invention preferably comprises the organotin compound, solvent, and resin described above. However, the semiconductor resist composition according to the above embodiment may optionally further contain additives. Examples of such additives include surfactants, crosslinking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0075] The surfactant may be, but is not limited to, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts, or combinations thereof.

[0076] 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. Preferably, the crosslinking agent is a compound having at least two crosslinking substituents. For example, compounds such as methoxymethylated glycoluryl, butoxymethylated glycoluryl, 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 can be preferably used.

[0077] Leveling agents are used to improve the flatness of the coating during printing, and commercially available, known leveling agents can be used.

[0078] The organic acid may be, but is not limited to, p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, fluorinated sulfonium salts, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or a combination thereof.

[0079] Specific examples of quenchers include, for example, diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or combinations thereof.

[0080] The amount of these additives used can be easily adjusted according to the desired physical properties, and they can also be omitted.

[0081] Furthermore, the above-mentioned semiconductor resist composition may be further used with a silane coupling agent as an adhesion enhancer to improve adhesion to the substrate (for example, to improve adhesion between the semiconductor resist composition and the substrate). Examples of silane coupling agents include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; or 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane; and carbon-carbon unsaturated bond-containing silane compounds such as trimethoxy[3-(phenylamino)propyl]silane.

[0082] The above semiconductor photoresist composition exhibits almost no 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, and such as a photoresist process using light with wavelengths of 5 nm to 20 nm, for example.

[0083] According to another embodiment of the present invention, a method for forming a pattern using the above-described semiconductor photoresist composition can be provided. For example, the manufactured pattern may be a photoresist pattern.

[0084] A pattern formation method according to one embodiment of the present invention includes the steps of: preparing a film to be etched on a substrate; applying the above-mentioned semiconductor photoresist composition on the film to be etched to form a photoresist film; patterning the photoresist film to form a photoresist pattern; and etching the film to be etched using the photoresist pattern as an etching mask.

[0085] 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 schematic cross-sectional diagrams illustrating a pattern formation method using the semiconductor photoresist composition according to the present invention.

[0086] Referring to Figure 1, first prepare the film to be etched. An example of the film to be etched may be a thin film 102 formed on a semiconductor substrate 100. The following explanation will only cover the case where the film to be etched is a thin film 102. To remove any contaminants remaining on the thin film 102, clean the surface of the thin film 102. The thin film 102 may be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film.

[0087] Next, a resist underlayer forming composition for providing a resist underlayer 104 on the surface of the cleaned thin film 102 is coated using a spin coating method. However, the present invention 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.

[0088] The above-mentioned coating step for the resist underlayer can be omitted, and the following section will describe the case where the resist underlayer is coated.

[0089] Subsequently, a drying and baking process is performed to form a resist underlayer film 104 on the thin film 102. The baking process can be carried out at 100 to 500°C, for example, at 100 to 300°C.

[0090] The resist underlayer 104 is provided between the substrate 100 and the photoresist film 106, and can prevent 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 areas, thereby preventing non-uniformity of the photoresist linewidth and interference with pattern formation.

[0091] Referring to Figure 2, the above-mentioned semiconductor photoresist composition is coated onto the resist underlayer film 104 to form a photoresist film 106. The photoresist film 106 may also be formed by coating the above-mentioned semiconductor photoresist composition onto a thin film 102 formed on the substrate 100, and then curing it through a heat treatment process.

[0092] More specifically, the step of forming a pattern using a semiconductor photoresist composition may include the steps of applying the above-mentioned 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.

[0093] Since the compositions for semiconductor photoresists have already been explained in detail, we will omit any redundant explanations.

[0094] 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 80°C to 120°C.

[0095] Referring to Figure 3, the photoresist film 106 is selectively exposed using a patterned mask 110.

[0096] For example, examples of light that can be used in the exposure process include not only short-wavelength light such as i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm), and ArF excimer laser (wavelength 193nm), but also high-energy wavelength light such as EUV (extreme ultraviolet; wavelength 13.5nm) and E-Beam (electron beam).

[0097] More specifically, the light used for exposure in one embodiment may be short-wavelength light having a wavelength range of 5 nm to 150 nm, or it may be light having a high-energy wavelength such as EUV (extreme ultraviolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0098] The exposed region 106b in the photoresist film 106 forms a polymer through crosslinking reactions such as condensation between organometallic compounds, thereby having a different solubility from the unexposed region 106a of the photoresist film 106.

[0099] Next, a second baking process is performed on the substrate 100. The second baking process can be carried out at a temperature of 90°C to 200°C. By performing the second baking process, the exposed region 106b of the photoresist film 106 becomes less soluble in the developer.

[0100] Figure 4 shows the photoresist pattern 108 formed by dissolving and removing the photoresist film 106a corresponding to the unexposed region using a developer. Specifically, the photoresist pattern 108 corresponding to the negative tone image is completed by dissolving and then removing the photoresist film 106a corresponding to the unexposed region using an organic solvent such as 2-heptanone.

[0101] As described above, the developer used in the pattern forming method according to one embodiment of the present invention may be an organic solvent. Examples of organic solvents used in the pattern forming 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; or combinations thereof.

[0102] However, the photoresist pattern according to one embodiment of the present invention is not necessarily limited to being formed as a negative tone image, but may be formed to have a positive tone image. In this case, examples of developers that can be used to form a positive tone image include quaternary ammonium hydroxide compositions such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof.

[0103] As described above, the photoresist pattern 108 formed by exposure with light having wavelengths such as i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm), and ArF excimer laser (wavelength 193nm), as well as high-energy light such as EUV (extreme ultraviolet; wavelength 13.5nm) and E-Beam (electron beam), can have a width of 5nm to 100nm. For example, the photoresist pattern 108 can be formed with widths of 5nm to 90nm, 5nm to 80nm, 5nm to 70nm, 5nm to 60nm, 5nm to 50nm, 5nm to 40nm, 5nm to 30nm, and 5nm to 20nm.

[0104] On the other hand, the photoresist pattern 108 can have 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 pitch having a line width roughness of, for example 10 nm or less, 5 nm or less, 3 nm or less, or 2 nm or less.

[0105] Next, the photoresist pattern 108 is used as an etching mask to etch the resist underlayer film 104. The organic film pattern 112 is formed through this etching process. The formed organic film pattern 112 can also have a width corresponding to the photoresist pattern 108.

[0106] 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 102 is formed as a thin film pattern 114.

[0107] 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.

[0108] In the previously performed exposure process, the thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process using an EUV light source can have a width corresponding to that of the photoresist pattern 108. For example, it can have a width of 5 nm to 100 nm, 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]

[0109] The present invention will be described in more detail below through examples relating to the manufacture of the semiconductor photoresist composition described above. However, the technical features of the present invention are not limited by the following examples.

[0110] (Synthesis of organotin compounds) (Synthesis Example 1) 2-hydroxyisobutyric acid (23.7 g, 228 mmol) was placed in a 1000 mL round-bottom flask, and 300 mL of toluene was added. A solution of mono-tert-butyltin tripionate (30 g, 76 mmol) dissolved in 100 mL of toluene was gradually added dropwise to the round-bottom flask, and the mixture was stirred at room temperature (25°C) for 2 hours. After vacuum drying at room temperature (25°C), a white solid was obtained. The obtained white solid was washed multiple times with dichloromethane and n-hexane, and then vacuum dried again to obtain the compound represented by the following chemical formula 1a.

[0111] [ka]

[0112] (Synthesis Example 2) The compound represented by the following chemical formula 2a was obtained by the same method as in Synthesis Example 1, except that lactic acid (20.5 g, 228 mmol) was used instead of 2-hydroxyisobutyric acid (23.7 g, 228 mmol).

[0113] [ka]

[0114] (Synthesis Example 3) The compound represented by the following chemical formula 5a was obtained by the same method as in Synthesis Example 1, except that glycolic acid (17.3 g, 228 mmol) was used instead of 2-hydroxyisobutyric acid (23.7 g, 228 mmol) and isopropylbutyltin tripionate (29.0 g, 76 mmol) was used instead of monotert-butyltin tripionate (30 g, 76 mmol).

[0115] [ka]

[0116] (Synthesis Example 4) The compound represented by the following chemical formula 6a was obtained by the same method as in Synthesis Example 1, except that glycolic acid (17.3 g, 228 mmol) was used instead of 2-hydroxyisobutyric acid (23.7 g, 228 mmol) and monobenzyltin tripionate (32.6 g, 76 mmol) was used instead of monotert-butyltin tripionate (30 g, 76 mmol).

[0117] [ka]

[0118] (Comparative Synthesis Example 1) In a 100 mL round-bottom flask, iPrSnPh3 (25.44 mmol, 10 g) and acetic acid (76.31 mmol, 4.6 g) were dissolved in 35 mL of acetonitrile and heated under reflux for 24 hours. The mixture was then vacuum-dried to completely remove the solvent and obtain the compound represented by the following chemical formula b in 80% yield.

[0119] [ka]

[0120] (Comparative Synthesis Example 2) Anhydrous hexane was placed in a 100 mL round-bottom flask, and LiNMe2 (102.03 mmol, 5.2 g) was dissolved in it. The flask was then cooled to -78°C. Isopropyl tin trichloride (34.01 mmol, 9.1 g) was gradually added dropwise, and the mixture was reacted at room temperature (25°C) for 24 hours. After the reaction was complete, the mixture was filtered, concentrated, and then vacuum-dried to obtain the compound represented by the following chemical formula c in 65% yield.

[0121] [ka]

[0122] (Examples 1-4, Comparative Example 1 and Comparative Example 2: Production of compositions for semiconductor photoresists) The compounds obtained in Synthesis Examples 1 to 4, Comparative Synthesis Example 1, and Comparative Synthesis Example 2 were each dissolved in 1-methyl-2-propyl acetate to a concentration of 3% by mass, and filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to produce semiconductor photoresist compositions.

[0123] <Evaluation 1: Stability against moisture> To analyze the extent of the changes caused by water, the tin compounds obtained in Synthesis Examples 1 to 4, Comparative Synthesis Example 1, and Comparative Synthesis Example 2 were dissolved in 1-methyl-2-propyl acetate solvent containing 1% by mass of water to a concentration of 10% by mass. Subsequently, the solution was... 119 Sn NMR measurements were performed, and the results were evaluated according to the following criteria, as shown in Table 1 below: *Evaluation criteria ◎: No changes were observed in the NMR peaks. ○: 1-29% of the total integral value changes. △: 30-89% of the total integral value changes. ×: More than 90% of the total integral value has changed.

[0124] <Evaluation 2: Sensitivity Evaluation> Fifty circular pad linear arrays with a diameter of 500 μm were projected onto wafers coated with the photoresist compositions of Examples 1-4 and Comparative Examples 1 and 2 using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). The pad exposure time was adjusted to ensure that an increasing dose of EUV was applied to each pad.

[0125] Subsequently, the resist and substrate were subjected to a post-exposure bake (PEB) on a hot plate at 160°C for 120 seconds. The baked films were then immersed in a developer (2-heptanone) for 30 seconds each, followed by an additional 10 seconds of washing with the same developer to form a negative tone image, i.e., to remove the unexposed coating areas. Finally, the process was completed by hot plate baking at 150°C for 2 minutes.

[0126] The residual resist thickness of the exposed pads was measured using a polarization measurement method (Ellipsometer). The residual resist thickness was measured for each exposure level and graphed as a function of exposure level. The Dg (energy level at which development is complete) for each type of resist was evaluated according to the following evaluation criteria and is shown in Table 1: *Evaluation criteria (Dg value) A: 16 mJ / cm² 2 less than B: 16 mJ / cm² 2 That's all.

[0127] [Table 1]

[0128] As is clear from the results in Table 1 above, the semiconductor photoresist compositions according to the examples can be confirmed to have superior stability against moisture and superior sensitivity compared to the comparative examples.

[0129] Although specific embodiments of the present invention have been described and illustrated above, it is obvious to those with ordinary skill in the art that the present invention is not limited to the described embodiments and can be modified and transformed in various ways without departing from the spirit and scope of the invention. Therefore, such modifications or variations should not be understood individually from the technical spirit or viewpoint of the present invention, and the modified embodiments should be said to fall within the scope of the claims of the present invention. [Explanation of Symbols]

[0130] 100 boards, 102 Thin film, 104 Resist underlayer film, 106 Photoresist film, 106a Unexposed area, 106b Exposed region, 108 photoresist patterns, 110 patterned masks, 112 Organic film patterns, 114 thin film patterns.

Claims

1. The organotin compounds represented by the following chemical formula 1; and solvent A composition for semiconductor photoresists, including: 【Chemistry 1】 In the aforementioned chemical formula 1, R １ ~R ６ Each of these is independently a halogen atom, a substituted or unsubstituted C1-C20 alkyl 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. R ７ These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C3-C20 cycloalkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C3-C20 cycloalkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof.

2. R in the above chemical formula 1 ７ The semiconductor photoresist composition according to claim 1, wherein is a substituted alkyl group having 1 to 20 carbon atoms.

3. R in the above chemical formula 1 １ ~R ６ The semiconductor photoresist composition according to claim 1, wherein each of them is independently a substituted or unsubstituted C1-C20 alkyl 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.

4. R in the above chemical formula 1 １ ~R ６ The semiconductor photoresist composition according to claim 1, wherein each of the groups is independently a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an iso-propyl group, an iso-butyl group, an iso-pentyl group, an iso-hexyl group, an iso-heptyl group, an iso-octyl group, an iso-nonyl group, an iso-decyl group, an iso-butyl group, an iso-pentyl group, an iso-hexyl group, an iso-heptyl group, an iso-octyl group, an iso-decyl group, an iso-decyl group, an iso-butyl group, an iso-pentyl group, an iso-hexyl group, an iso-heptyl group, an iso-octyl group, an iso-decyl group, an iso-decyl group, an iso-decyl group, an iso-propyl group, an n-butyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-decyl group, or an n-decyl group.

5. R in the chemical formula 1 １ ~R ６ Among them, at least one is a substituted or unsubstituted alkyl group having 1 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. The composition for a semiconductor photoresist according to claim 1.

6. R in the above chemical formula 1 １ and R ２ At least one of the R in the chemical formula 1 ３ and R ４ At least one of the above, and R in the chemical formula 1 ５ and R ６ The semiconductor photoresist composition according to claim 1, wherein at least one of the groups is a substituted or unsubstituted C1-C20 alkyl 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.

7. The semiconductor photoresist composition according to claim 1, wherein the organotin compound is a compound represented by the following chemical formula 1a. 【Chemistry 2】

8. The semiconductor photoresist composition according to claim 1, wherein the content of the organotin compound is 1% to 30% by mass, based on 100% by mass of the total mass of the semiconductor photoresist composition.

9. 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.

10. The stage of preparing the film to be etched on the substrate; A step of forming a photoresist film by applying the semiconductor photoresist composition according to any one of claims 1 to 9 onto the film to be etched; The step of patterning the photoresist film to form a photoresist pattern; and A pattern formation method comprising the step of etching a film to be etched using the aforementioned photoresist pattern as an etching mask.

11. The pattern formation method according to claim 10, wherein the step of forming the photoresist pattern uses light with a wavelength of 5 nm to 150 nm.

12. The pattern forming method according to claim 10, further comprising the step of forming a resist underlayer film between the substrate and the photoresist film.

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

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