Semiconductor photoresist composition and method for forming a pattern using the same

Abstract

To provide a semiconductor photoresist composition with improved storage stability and coating performance.SOLUTION: The present invention provides a semiconductor photoresist composition that contains an organotin compound represented by a chemical formula 1 and a solvent, and a patterning method using the same.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 performing spatial resolution below 16 nm. Currently, traditional chemically amplified (CA) photoresists are being developed continuously to meet the specifications for resolution, light speed, feature roughness, and line edge roughness (LER) for next generation devices.

[0004] Intrinsic image blur due to acid-catalyzed reactions occurring in these polymeric photoresists limits resolution at small feature sizes, a fact that has long been known in electron beam (e-beam) lithography. Chemically amplified (CA) photoresists, although designed for high sensitivity, can experience additional difficulties under EUV exposure, in part because their typical elemental composition reduces the absorbance of the photoresist at 13.5 nm wavelengths, thereby reducing sensitivity.

[0005] CA photoresists can also experience difficulties with roughness issues at small feature sizes, and experiments have shown that line edge roughness (LER) increases as 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 new types of high performance photoresists.

[0006] In order to overcome the disadvantages of the above-mentioned chemically amplified organic photoresists, inorganic photoresists have been researched. Inorganic photoresists are mainly used for negative tone patterning, which is resistant to removal by developers due to chemical modification by a non-chemically amplified mechanism. Inorganic photoresists contain inorganic elements that have a higher EUV absorption rate than hydrocarbons, and are known to ensure high sensitivity even with a non-chemically amplified mechanism, have less stochastic effect, are sensitive, and have less line edge roughness and number of 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 bilayer configurations at deep UV, x-ray, and electron beam sources. More recently, impressive performance has been shown when using cationic hafnium metal oxide sulfate (HfSOx) materials with peroxo complexing agents to image 15 nm half pitch (HP) by projection EUV exposure (Patent Document 2 and Non-Patent Document 2). This system shows the best performance of non-CA photoresists and has a light speed approaching the requirements for a viable EUV photoresist. However, hafnium metal oxide sulfate materials with peroxo complexing agents have some practical disadvantages. First, the material is coated with a highly corrosive sulfuric acid / hydrogen peroxide mixture and has poor storage stability. Second, it is a complex mixture and cannot be easily modified to improve performance. Third, it must be developed with a very high concentration of TMAH (tetramethylammonium hydroxide) solution, such as 25% by weight.

[0009] Recently, it has become known that molecules containing tin have excellent extreme ultraviolet absorption, and active research is being conducted on them. In the case of organotin polymers, one of them, alkyl ligands are dissociated by light absorption or secondary electrons generated by it, and crosslinking with surrounding chains through iodine bonds enables negative tone patterning that is not removed by organic developers. Such organotin polymers have shown a dramatic improvement in sensitivity while maintaining resolution and line edge roughness, but further improvement in patterning properties is required for commercialization. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] U.S. Pat. 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] JK Stowers, A. Telecky, M. Kocsis, BL Clark, DA Keszler, A. Grenville, CN Anderson, PP Naulleau, 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 having improved storage stability and coating properties.

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

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

[0015] [ka]

[0016] In the above chemical formula 1, R 1is 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; R 2 , R 4 and R 5 each independently represents a hydrogen atom, a cyano group, a sulfonyl group, a thiol group, a sulfide group, a thioketone group, a ketone group, an aldehyde group, a hydroxy group, an amine group, an amide group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or a combination thereof; R 3 , R 6 and R 7 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; L 1 ~L 3each independently represents 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, -C(=O)-, -C(=S)-, or a combination thereof; m and n are each independently an integer from 0 to 3; m+n is an integer greater than or equal to 1.

[0017] The compound represented by Chemical Formula 1 above may be a compound represented by Chemical Formula 2 or 3 below.

[0018] [ka]

[0019] In the above Chemical Formula 2 and Chemical Formula 3, R 1 ~R 7 , and L 1 ~L 3 is defined as defined in Chemical Formula 1 above, m and n are each independently an integer of 1 to 3.

[0020] In the above Chemical Formula 2 and Chemical Formula 3, m and n can each independently be an integer of 1 or 2.

[0021] The compound represented by the above formula 2 may be a compound represented by the following formula 2-1.

[0022] [ka]

[0023] In the above chemical formula 2-1, R 1is 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; R 2a , R 2b and R 2c each independently represents a hydrogen atom, a cyano group, a sulfonyl group, a thiol group, a sulfide group, a thioketone group, a ketone group, an aldehyde group, a hydroxy group, an amine group, an amide group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or a combination thereof; R 3a , R 3b and R 3c 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; L 1a , L 1b and L 1care each independently 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, -C(=O)-, -C(=S)-, or a combination thereof.

[0024] The compound represented by the above formula 3 may be a compound represented by the following formula 3-1.

[0025] [ka]

[0026] In the above chemical formula 3-1, R 1 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; R 4a , R 4b , R 4c , R 5a , R 5b and R 5ceach independently represents a hydrogen atom, a cyano group, a sulfonyl group, a thiol group, a sulfide group, a thioketone group, a ketone group, an aldehyde group, a hydroxy group, an amine group, an amide group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or a combination thereof; R 6a , R 6b , R 6c , R 7a , R 7b and R 7c 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; L 2a , L 3a , L 2b , L 3b , L 2c and L 3c are each independently 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, -C(=O)-, -C(=S)-, or a combination thereof.

[0027] R in the above Chemical Formula 1 to Chemical Formula 3 1 may each independently be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0028] R in the above Chemical Formula 1 to Chemical Formula 3 2 , R 4 and R 5 may each independently be a hydrogen atom, a cyano group, a sulfonyl group, a thiol group, a sulfide group, a thioketone group, a ketone group, an aldehyde group, a hydroxy group, an amine group, an amide group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or a combination thereof.

[0029] R in the above Chemical Formula 1 to Chemical Formula 3 2 , R 4 and R 5 each independently represents a hydrogen atom, a cyano group, a sulfonyl group, a thiol group, a sulfide group, a thioketone group, a ketone group, an aldehyde group, a hydroxy group, an amine group, an amide group, a halogen 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 isopropyl group, an isobutyl group, an isopentyl group, an isohexyl group, an isoheptyl group, an isooctyl group, an isononyl group, an isodecyl group, or a se It can be a c-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, a tert-decyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzoxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted benzothiazolyl group, or a substituted or unsubstituted benzimidazolyl group.

[0030] L in the above Chemical Formulas 1 to 3 1 ~L 3may each independently be a single bond, or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms.

[0031] The organotin compound may be at least one selected from the group consisting of the compounds listed in Group 2 below.

[0032] [ka]

[0033] The content of the organotin compound may be 1% by mass to 30% by mass, based on 100% by mass of the composition for semiconductor photoresist.

[0034] The semiconductor photoresist composition may further include additives such as a surfactant, a crosslinking agent, a leveling agent, or a combination thereof.

[0035] A method for forming a pattern according to another embodiment of the present invention includes the steps of forming a film to be etched on a substrate, applying the above-described 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 by using the photoresist pattern as an etching mask.

[0036] The step of forming the photoresist pattern may use light having a wavelength of 5 nm to 150 nm.

[0037] The pattern forming method may further include a step of forming a resist underlayer film between the substrate and the photoresist film.

[0038] The photoresist pattern may have a width of 5 nm to 100 nm. Effect of the Invention

[0039] According to the present invention, a semiconductor photoresist composition having improved storage stability and coating properties can be provided. [Brief description of the drawings]

[0040] [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. [Diagram 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. [Diagram 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. [Diagram 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 PREFERRED EMBODIMENTS

[0041] Hereinafter, an embodiment of the present invention will be described in detail with reference to the accompanying drawings. However, in describing the present invention, a description of already known functions or configurations will be omitted in order to clarify the gist of the present invention.

[0042] In order to clearly explain the present invention, parts unnecessary for the explanation are omitted, and the same or similar components are given 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.

[0043] In the drawings, the thickness of a plurality of layers and regions is exaggerated to clearly show the layers and regions. Also, in the drawings, the thickness of some layers and regions is exaggerated for the convenience of explanation. When a layer, film, region, plate, or other part is said to be "on" another part, this includes not only the case where it is "directly on" the other part, but also the case where there is another part therebetween.

[0044] In this specification, "substituted" means that a hydrogen atom is replaced with a deuterium atom, a halogen atom, a hydroxy group, a cyano group, a sulfonyl group, a thiol group, a sulfide group, a thioketone group, a ketone group, an aldehyde group, an amide group, a nitro group, -NRR' (wherein R and R' are each independently hydrogen, a substituted or unsubstituted saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted saturated or unsaturated alicyclic hydrocarbon group having 3 to 30 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms), -SiRR'R" (wherein R, R' and R" each independently represent 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), an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a combination thereof.

[0045] By "unsubstituted" it is meant that the hydrogen atom remains a hydrogen atom without being replaced by another substituent.

[0046] As used herein, unless otherwise specified, the term "alkyl group" refers to a straight or branched chain aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0047] The alkyl group can be an alkyl group having 1 to 10 carbon atoms. For example, the alkyl group can 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 can 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.

[0048] Unless otherwise defined, the term "cycloalkyl group" used herein means a monovalent cyclic aliphatic saturated hydrocarbon group.

[0049] The cycloalkyl group can 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 can be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, but is not limited to these.

[0050] As used herein, an "aryl group" refers to a substituent in which all elements of the cyclic substituent have p-orbitals and these p-orbitals form a conjugated structure, including monocyclic or fused polycyclic (i.e., rings which share adjacent pairs of carbon atoms) functional groups.

[0051] As used herein, unless otherwise defined, the term "alkenyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group, an aliphatic unsaturated alkenyl group containing one or more double bonds.

[0052] As used herein, unless otherwise defined, the term "alkynyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group, an aliphatic unsaturated alkynyl group containing one or more triple bonds.

[0053] In the formulae depicted herein, t-Bu refers to a tert-butyl group.

[0054] Hereinafter, a semiconductor photoresist composition according to one embodiment of the present invention will be described.

[0055] A composition for semiconductor photoresist according to one embodiment of the present invention includes an organotin compound represented by the following Formula 1 and a solvent.

[0056] [ka]

[0057] In the above chemical formula 1, R 1 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; R 2 , R 4 and R 5 each independently represents a hydrogen atom, a cyano group, a sulfonyl group, a thiol group, a sulfide group, a thioketone group, a ketone group, an aldehyde group, a hydroxy group, an amine group, an amide group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or a combination thereof; R 3 , R 6 and R 7each 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; L 1 ~L 3 each independently represents 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, -C(=O)-, -C(=S)-, or a combination thereof; m and n are each independently an integer from 0 to 3; m+n is an integer greater than or equal to 1.

[0058] The above-mentioned organotin compound contains at least one bidentate ligand directly bonded to Sn, and thus has a bidentate or more coordinate bond sheet, and the unshared electron pair induces not only intermolecular bonds but also intramolecular coordinate bonds, which is advantageous for the formation of an amorphous matrix. Note that "having a bidentate or more coordinate bond sheet" means that the additional coordinate sites derived from the bidentate ligand are bidentate or more.

[0059] In particular, compared to the tetravalently coordinated cluster form, the coordination number of Sn is filled by additional coordination bonds, resulting in a structure in which Sn atoms are hidden, improving stability against moisture and preventing the aggregation phenomenon caused by nucleation induced by oxygen contained in the cluster, thereby improving long-term storage stability. Therefore, defects are effectively reduced during the coating process, which also affects coating stability.

[0060] Furthermore, compared to organotin compounds containing only monodentate ligands, the adhesion to the substrate is improved due to stronger intermolecular or intramolecular bonds, and the thin film stability can also be improved.

[0061] In addition, since the aggregation phenomenon due to nucleation is prevented, the material can be coated in an amorphous form without using any additives during spin coating, thereby improving sensitivity and coatability.

[0062] The organotin compound represented by the above Chemical Formula 1 may be a compound represented by the following Chemical Formula 2 or Chemical Formula 3.

[0063] [ka]

[0064] In the above Chemical Formula 2 and Chemical Formula 3, R 1 ~R 7 , and L 1 ~L 3 is defined as defined in Chemical Formula 1 above, m and n are each independently an integer of 1 to 3.

[0065] m and n may each independently be an integer of 1 or 2.

[0066] The compound represented by the above formula 2 may be a compound represented by the following formula 2-1.

[0067] [ka]

[0068] In the above chemical formula 2-1, R 1is 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; R 2a , R 2b and R 2c each independently represents a hydrogen atom, a cyano group, a sulfonyl group, a thiol group, a sulfide group, a thioketone group, a ketone group, an aldehyde group, a hydroxy group, an amine group, an amide group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or a combination thereof; R 3a , R 3b and R 3c 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; L 1a , L 1b and L 1care each independently 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, -C(=O)-, -C(=S)-, or a combination thereof.

[0069] The organotin compound represented by the above formula 3 may be a compound represented by the following formula 3-1.

[0070] [ka]

[0071] In the above chemical formula 3-1, R 1 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; R 4a , R 4b , R 4c , R 5a , R 5b and R 5ceach independently represents a hydrogen atom, a cyano group, a sulfonyl group, a thiol group, a sulfide group, a thioketone group, a ketone group, an aldehyde group, a hydroxy group, an amine group, an amide group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or a combination thereof; R 6a , R 6b , R 6c , R 7a , R 7b and R 7c 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; L 2a , L 3a , L 2b , L 3b , L 2c and L 3c are each independently 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, -C(=O)-, -C(=S)-, or a combination thereof.

[0072] R in the above Chemical Formula 1 to Chemical Formula 3 1 can be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0073] In one embodiment of the present invention, R 1 can be n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, iso-propyl, iso-butyl, iso-pentyl, iso-hexyl, iso-heptyl, iso-octyl, iso-nonyl, iso-decyl, sec-butyl, sec-pentyl, sec-hexyl, sec-heptyl, sec-octyl, tert-butyl, tert-pentyl, tert-hexyl, tert-heptyl, tert-octyl, tert-nonyl, or tert-decyl.

[0074] In one embodiment of the present invention, R 2 , R 4 and R 5 may each independently be a hydrogen atom, a cyano group, a sulfonyl group, a thiol group, a sulfide group, a thioketone group, a ketone group, an aldehyde group, a hydroxy group, an amine group, an amide group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or a combination thereof.

[0075] As a specific example, R 2 , R 4 and R 5each independently represents a hydrogen atom, a cyano group, a sulfonyl group, a thiol group, a sulfide group, a thioketone group, a ketone group, an aldehyde group, a hydroxy group, an amine group, an amide group, a halogen 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 isopropyl group, an isobutyl group, an isopentyl group, an isohexyl group, an isoheptyl group, an isooctyl group, an isononyl group, an isodecyl group, or a se It can be a c-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, a tert-decyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzoxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted benzothiazolyl group, or a substituted or unsubstituted benzimidazolyl group.

[0076] As an example, L in the above Chemical Formula 1 to Chemical Formula 3 1 ~L 3 may each independently be a single bond, or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms.

[0077] In one embodiment of the present invention, L in Chemical Formula 1 to Chemical Formula 3 1 ~L 3 may each independently be a single bond, a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted trimethylene group, or a substituted or unsubstituted propylene group.

[0078] As a more specific example, the organotin compound according to the present invention may be a compound represented by the above chemical formula 2-1.

[0079] Precursors of the bidentate ligand include 2-hydroxyiminocarboxylate compounds, 2-methoxyiminocarboxylate compounds, and the like, and may be selected from, for example, the compounds listed in Group 1 below.

[0080] [ka]

[0081] More specific examples of the organotin compound include the compounds listed in Group 2 below.

[0082] [ka]

[0083] For example, the organotin compound may be a compound represented by Chemical Formula 2 above.

[0084] As a more specific example, the organotin compound may be a compound represented by the above formula 2-1.

[0085] The above organotin compound strongly absorbs extreme ultraviolet light with a wavelength of 13.5 nm and has excellent sensitivity to light having high energy.

[0086] According to one embodiment of the present invention, the organotin compound may be contained in an amount of 1% by mass to 30% by mass, for example, 1% by mass to 25% by mass, for example, 1% by mass to 20% by mass, for example, 1% by mass to 15% by mass, for example, 1% by mass to 10% by mass, for example, 1% by mass to 5% by mass, but is not limited thereto. When the organotin compound is contained in an amount within the above range, the storage stability and etching resistance of the semiconductor photoresist composition are improved, and the resolution characteristics are improved.

[0087] The above-mentioned organotin compounds 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.

[0088] The composition for semiconductor photoresist according to one embodiment of the present invention may have excellent sensitivity and pattern formability by including the organotin compound described above.

[0089] The solvent included in the semiconductor photoresist composition according to one embodiment of the present invention may be an organic solvent, examples of which include, but are not limited to, aromatic compounds (e.g., xylene, toluene), alcohols (e.g., 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropyl alcohol, 1-propanol), ethers (e.g., anisole, tetrahydrofuran), esters (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate), ketones (e.g., methyl ethyl ketone, 2-heptanone), mixtures thereof, and the like.

[0090] In one embodiment of the present invention, the semiconductor photoresist composition may further include a resin in addition to the organotin compound and the solvent.

[0091] The resin can be a phenolic resin that contains at least one aromatic moiety listed in Group 3 below.

[0092] [ka]

[0093] The resin may have a weight average molecular weight of 500 to 20,000. The "weight average molecular weight" can be measured by gel permeation chromatography (GPC).

[0094] 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 photoresist composition.

[0095] When the resin is contained within the above content range, excellent etching resistance and heat resistance can be obtained.

[0096] Meanwhile, the semiconductor photoresist composition according to one embodiment of the present invention preferably comprises the above-mentioned organotin compound, solvent, and resin. However, the semiconductor photoresist composition according to the above-mentioned embodiment may further include additives, if necessary. Examples of additives include surfactants, crosslinking agents, leveling agents, organic acids, inhibitors (quenchers), or combinations thereof.

[0097] The surfactant may be, for example, but is not limited to, an alkylbenzenesulfonate, an alkylpyridinium salt, a polyethylene glycol, a quaternary ammonium salt, or a combination thereof.

[0098] Examples of the crosslinking agent include, but are not limited to, melamine-based crosslinking agents, substituted urea-based crosslinking agents, acrylic-based crosslinking agents, epoxy-based crosslinking agents, or polymer-based crosslinking agents. Examples of the crosslinking agent having at least two crosslinking-forming substituents 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, or methoxymethylated thiourea.

[0099] The leveling agent is used to improve the coating flatness during application (printing), and any known leveling agent that is commercially available can be used.

[0100] The organic acid can be, but is not limited to, p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, sulfonium fluorides, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or combinations thereof.

[0101] The inhibitor (quencher) can be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or combinations thereof.

[0102] The amounts of these additives used can be easily adjusted depending on the desired physical properties, and they can also be omitted.

[0103] In addition, the semiconductor photoresist composition can further use a silane coupling agent as an adhesion improver to improve adhesion to the substrate (for example, to improve adhesion between the semiconductor photoresist composition and the substrate). Examples of the silane coupling agent include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; and silane compounds containing carbon-carbon unsaturated bonds such as trimethoxy[3-(phenylamino)propyl]silane.

[0104] The semiconductor photoresist composition can prevent pattern collapse even when a pattern having a high aspect ratio is formed. Therefore, in order 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, for example, 5 nm to 80 nm, for example, a fine pattern having a width of, for example, 5 nm to 70 nm, for example, a fine pattern having a width of, for example, 5 nm to 50 nm, for example, a fine pattern having a width of, for example, 5 nm to 40 nm, for example, a fine pattern having a width of, for example, 5 nm to 30 nm, for example, a fine pattern having a width of, for example, 5 nm to 20 nm, the composition can be used in a photoresist process using light having a wavelength of, for example, 5 nm to 150 nm, for example, a photoresist process using light having a wavelength of, for example, 5 nm to 100 nm, for example, a photoresist process using light having a wavelength of, for example, 5 nm to 80 nm, for example, a photoresist process using light having a wavelength of, for example, 5 nm to 50 nm, for example, a photoresist process using light having a wavelength of, for example, 5 nm to 30 nm, for example, a photoresist process using light having a wavelength of, for example, 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.

[0105] Meanwhile, according to another embodiment of the present invention, there may be provided a method for forming a pattern using the above-mentioned semiconductor photoresist composition. For example, the formed pattern may be a photoresist pattern.

[0106] A method for forming a pattern according to an embodiment of the present invention includes the steps of forming a film to be etched on a substrate, applying the above-described 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 by using the photoresist pattern as an etching mask.

[0107] A method for forming a pattern using the above-mentioned semiconductor photoresist composition will be described below with reference to Figures 1 to 5. Figures 1 to 5 are schematic cross-sectional views for explaining a method for forming a pattern using the semiconductor photoresist composition according to the present invention.

[0108] 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. Hereinafter, only the case where the object to be etched is the thin film 102 will be described. 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.

[0109] Next, a composition for forming a resist underlayer film for forming a resist underlayer film 104 is coated on the surface of the cleaned thin film 102 by applying a spin coating method. However, the present invention is not necessarily limited to this, and various known coating methods, such as spray coating, dip coating, knife edge coating, and printing methods, such as inkjet printing and screen printing, can also be used.

[0110] Although the step of coating the resist underlayer film can be omitted, the following describes the case where the resist underlayer film is coated.

[0111] 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 a temperature of 100 to 500°C, for example, at a temperature of 100 to 300°C.

[0112] The resist underlayer film 104 is formed between the substrate 100 and the photoresist film 106 to prevent non-uniformity of the photoresist line width and disruption of pattern formability when radiation reflected from the interface between the substrate 100 and the photoresist film 106 or from an interlayer hard mask is scattered into unintended photoresist regions.

[0113] 2, the above-described semiconductor photoresist composition is coated on a resist underlayer film 104 to form a photoresist film 106. The photoresist film 106 may be in a form obtained by coating the above-described semiconductor photoresist composition on a thin film 102 formed on a substrate 100 and then hardening the composition through a heat treatment process.

[0114] More specifically, the process of forming a pattern using the semiconductor photoresist composition may include a process of applying the semiconductor photoresist composition of the present invention onto the substrate 100 on which the thin film 102 is formed by spin coating, slit coating, inkjet printing, or the like, and a process of drying the applied semiconductor photoresist composition to form a photoresist film 106.

[0115] The semiconductor photoresist composition has already been described in detail, so a duplicated description will be omitted.

[0116] 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 in the range of 80°C to 120°C.

[0117] Referring to FIG. 3, the photoresist film 106 is selectively exposed to light.

[0118] As an example, examples of light that can be used in the 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).

[0119] More specifically, the exposure light according to an embodiment may be short-wavelength light having a wavelength range of 5 nm to 150 nm, and may be light having a high-energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0120] The exposed regions 106b of the photoresist film 106 form polymers through a crosslinking reaction such as condensation between organometallic compounds, and thus have a different solubility from the unexposed regions 106a of the photoresist film 106.

[0121] Next, a second baking process is performed on the substrate 100. The second baking process can be performed 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 difficult to dissolve in a developer.

[0122] 4 shows a photoresist pattern 108 formed by dissolving and removing the photoresist film 106a corresponding to the unexposed region using a developer. Specifically, the photoresist film 106a corresponding to the unexposed region is dissolved and removed using an organic solvent such as 2-heptanone, thereby completing the photoresist pattern 108 corresponding to a negative tone image.

[0123] As described above, the developer used in the pattern formation method according to an embodiment of the present invention may be an organic solvent. Examples of the organic solvent used include ketones such as methyl ethyl ketone, acetone, cyclohexanone, and 2-heptanone, alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, and methanol, esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, and butyrolactone, aromatic compounds such as benzene, xylene, and toluene, or combinations thereof.

[0124] 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 also be formed to have a positive tone image. In this case, examples of developers that can be used to form a positive tone image include quaternary ammonium hydroxide compositions such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof.

[0125] As described above, the photoresist pattern 108 formed by exposure to light having a wavelength such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), 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) may have a width of 5 nm to 100 nm. As an example, the photoresist pattern 108 may be formed with 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.

[0126] On the other hand, the photoresist pattern 108 may have a pitch with a half pitch of 50 nm or less, such as 40 nm or less, such as 30 nm or less, such as 20 nm or less, such as 15 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.

[0127] Next, the resist underlayer film 104 is etched using the photoresist pattern as an etching mask. Through the above-mentioned etching process, an organic film pattern 112 is formed. The formed organic film pattern 112 may also have a width corresponding to the photoresist pattern .

[0128] 5, the photoresist pattern 108 is applied as an etching mask to etch the exposed thin film 102. As a result, the thin film is formed into a thin film pattern 114.

[0129] The thin film 102 can be etched by dry etching using an etching gas such as CHF3, CF4, Cl2, BCl3, or a mixture thereof.

[0130] The thin film pattern 114 formed by utilizing the photoresist pattern 108 formed by the exposure process performed using an EUV light source in the previous exposure process may have a width corresponding to the photoresist pattern 108. As an 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 may be formed with a width of 20 nm or less. EXAMPLES

[0131] The present invention will be described in more detail below with reference to examples of the preparation of the above-mentioned semiconductor photoresist composition, but the technical features of the present invention are not limited to the following examples.

[0132] (Synthesis of organotin compounds) (Synthesis Example 1) Pyruvic acid (7.92 g, 90 mmol) was placed in a 250 mL two-neck round-bottom flask and 100 mL of water was added. Then, hydroxylamine hydrochloride (6.25 g, 90 mmol) was gradually added dropwise at room temperature, followed by ammonium bicarbonate (14.22 g, 180 mmol) and stirring for 2 hours. Then, butyltin trichloride (8.46 g, 30 mmol) was added dropwise at room temperature and stirred for 4 hours. After vacuum filtration, the mixture was washed several times with ice water and vacuum dried at room temperature to obtain a compound represented by the following chemical formula 4.

[0133] [ka]

[0134] (Synthesis Example 2) A compound represented by the following formula 5 was obtained by the same synthesis method as in Synthesis Example 1, except that phenylpyruvic acid (14.77 g, 90 mmol) was used instead of pyruvic acid (7.92 g, 90 mmol).

[0135] [ka]

[0136] (Synthesis Example 3) A compound represented by the following chemical formula 6 was obtained by synthesizing in the same manner as in Synthesis Example 1, except that 2-(methoxyimino)propionic acid (10.54 g, 90 mmol) was used instead of pyruvic acid (7.92 g, 90 mmol).

[0137] [ka]

[0138] (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, yielding a compound represented by the following chemical formula 7.

[0139] [ka]

[0140] (Comparative Synthesis Example 2) LiNMe2 (102.03 mmol, 5.2 g) was dissolved in anhydrous hexane in a 100 mL round-bottom flask and the flask was cooled to -78°C. Isopropyltin trichloride (34.01 mmol, 10 g) was slowly added dropwise and reacted at room temperature for 24 hours. After the reaction was completed, the mixture was filtered, concentrated, and dried in vacuum to obtain a compound represented by the following chemical formula 8.

[0141] [ka]

[0142] (Examples 1 to 3, Comparative Examples 1 and 2: Production of Semiconductor Photoresist Compositions) The compounds obtained in Synthesis Examples 1 to 3, Comparative Synthesis Examples 1 and 2 were dissolved in 4-methyl-2-pentanol at a concentration of 3 mass % and filtered using a 0.1 μm PTFE syringe filter to prepare photoresist compositions.

[0143] (Photoresist film formation) A 4-inch diameter circular silicon wafer having a native oxide surface was used as a substrate for thin film deposition, and the wafer was treated in a UV ozone cleaning system for 10 minutes before depositing a thin film. The semiconductor photoresist compositions according to Examples 1 to 3, Comparative Examples 1 and 2 were spin-coated on the treated substrate at 1500 rpm for 30 seconds, and baked (post-baked, PAB) at 100° C. for 120 seconds to form a thin film.

[0144] Thereafter, the thickness of the film after coating and baking was measured by ellipsometry, and it was 25 nm for Examples 1 to 3, and 20 nm for Comparative Examples 1 and 2.

[0145] (Evaluation 1: Evaluation of coating properties) The surface roughness (Rq value) of the photoresist films prepared by the above coating methods according to Examples 1 to 3 and Comparative Examples 1 and 2 was measured using an AFM (atomic force microscope). The results according to the following evaluation criteria are shown in Table 1 below: Evaluation criteria ○: 0.5nm or less △: Over 0.5 nm and under 1 nm ×: More than 1 nm.

[0146] (Evaluation 2: Evaluation of storage stability) The photoresist compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated for initial sensitivity and the degree of precipitation after leaving the compositions at room temperature (0°C to 30°C) by the naked eye. The storage standards were set as follows and rated into three stages: Storage criteria ○: Can be stored for 3 months or more △: Can be stored for 2 weeks or more but less than 3 months ×: Can be stored for less than 2 weeks.

[0147] [Table 1]

[0148] From the results in Table 1 above, it is expected that the semiconductor photoresist compositions of Examples 1 to 3 have excellent coating properties and storage stability, and that the patterns formed therefrom have excellent sensitivity, although the line edge roughness is not significantly increased, compared to Comparative Examples 1 and 2.

[0149] Although specific embodiments of the present invention have been described and illustrated above, it is obvious to those skilled in the art that the present invention is not limited to the described embodiments, and that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modifications or variations should not be understood individually from the technical spirit and perspective of the present invention, and the modified embodiments should be considered to belong to the scope of the claims of the present invention. [Explanation of symbols]

[0150] 100 boards, 102 Thin Films, 104 Resist underlayer film, 106 Photoresist film, 106a unexposed area, 106b exposed area; 108 Photoresist pattern, 112 Organic film pattern, 114 Thin film pattern.

Claims

1. An organotin compound represented by the following chemical formula 1: solvent A composition for a semiconductor photoresist, comprising: 【Chemistry 1】 In the above Chemical Formula 1, R １ 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; R ２ , R ４ and R ５ each independently represents a hydrogen atom, a cyano group, a sulfonyl group, a thiol group, a sulfide group, a thioketone group, a ketone group, an aldehyde group, a hydroxy group, an amine group, an amide group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or a combination thereof; R ３ , R ６ and R ７ 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; L １ ~L ３ each independently represents 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 containing one or more double bonds or triple bonds and having 2 to 20 carbon atoms, a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, -C(=O)-, -C(=S)-, or a combination thereof; m and n are each independently an integer from 0 to 3; m+n is an integer of 1 or greater.

2. 2. The composition for semiconductor photoresist according to claim 1, wherein the organotin compound represented by Chemical Formula 1 is a compound represented by the following Chemical Formula 2 or Chemical Formula 3: 【Chemistry 2】 In the above Chemical Formula 2 and Chemical Formula 3, R １ ~R ７ , and L １ ~L ３ is defined as defined in Chemical Formula 1 above, m and n are each independently an integer from 1 to 3.

3. 3. The composition for semiconductor photoresist according to claim 2, wherein m in Formula 2 and n in Formula 3 are each independently an integer of 1 or 2.

4. The compound represented by Chemical Formula 2 is a compound represented by the following Chemical Formula 2-1: 【Chemistry 3】 In the above Chemical Formula 2-1, R １ 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; R ２ａ , R ２ｂ and R ２ｃ each independently represents a hydrogen atom, a cyano group, a sulfonyl group, a thiol group, a sulfide group, a thioketone group, a ketone group, an aldehyde group, a hydroxy group, an amine group, an amide group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or a combination thereof; R ３ａ , R ３ｂ and R ３ｃ 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; L １ａ , L １ｂ and L １ｃ are each independently 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 containing one or more double bonds or triple bonds and having 2 to 20 carbon atoms, a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, -C(=O)-, -C(=S)-, or a combination thereof.

5. 3. The composition for semiconductor photoresist according to claim 2, wherein the organotin compound represented by Chemical Formula 3 is a compound represented by Chemical Formula 3-1 below: 【Chemistry 4】 In the above Chemical Formula 3-1, R １ 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; R ４ａ , R ４ｂ , R ４ｃ , R ５ａ , R ５ｂ and R ５ｃ each independently represents a hydrogen atom, a cyano group, a sulfonyl group, a thiol group, a sulfide group, a thioketone group, a ketone group, an aldehyde group, a hydroxy group, an amine group, an amide group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or a combination thereof; R ６ａ , R ６ｂ , R ６ｃ , R ７ａ , R ７ｂ and R ７ｃ 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 cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkynyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof; L ２ａ , L ３ａ , L ２ｂ , L ３ｂ , L ２ｃ and L ３ｃ are each independently 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 containing one or more double bonds or triple bonds and having 2 to 20 carbon atoms, a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, -C(=O)-, -C(=S)-, or a combination thereof.

6. R in Formula 1 １ 2. The semiconductor photoresist composition according to claim 1, wherein is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

7. R in Formula 1 ２ , R ４ and R ５ wherein each independently represents a hydrogen atom, a cyano group, a sulfonyl group, a thiol group, a sulfide group, a thioketone group, a ketone group, an aldehyde group, a hydroxyl group, an amine group, an amide group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or a combination thereof.

8. R in Formula 1 ２ , R ４ and R ５ each independently represents a hydrogen atom, a cyano group, a sulfonyl group, a thiol group, a sulfide group, a thioketone group, a ketone group, an aldehyde group, a hydroxy group, an amine group, an amide group, a halogen 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 isopropyl group, an isobutyl group, an isopentyl group, an isohexyl group, an isoheptyl group, an isooctyl group, an isononyl group, an isodecyl group, a sec-butyl group, a sec 2. The semiconductor photoresist composition according to claim 1, wherein the aryl group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzoxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted benzothiazolyl group, or a substituted or unsubstituted benzimidazolyl group.

9. L in Formula 1 １ ~L ３ The semiconductor photoresist composition according to claim 1, wherein each of the groups independently represents a single bond or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms.

10. 2. The semiconductor photoresist composition according to claim 1, wherein the organotin compound is at least one selected from the group consisting of the compounds listed in Group 2 below. 【Chemistry 5】

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

12. 10. The semiconductor photoresist composition of claim 1, further comprising an additive selected from the group consisting of a surfactant, a crosslinking agent, a leveling agent, and combinations thereof.

13. forming a film to be etched on a substrate; A step of applying a composition for semiconductor photoresist according to any one of claims 1 to 12 onto 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.

14. 14. The pattern forming method according to claim 13, wherein the step of forming the photoresist pattern comprises using light having a wavelength of 5 nm to 150 nm.

15. The pattern forming method according to claim 13, further comprising the step of forming a resist underlayer film between the substrate and the photoresist film.

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

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