KR-20260064282-A - SEMICONDUCTOR PHOTORESIST COMPOSITION AND METHOD OF FORMING PATTERNS USING THE COMPOSITION

KR20260064282AKR 20260064282 AKR20260064282 AKR 20260064282AKR-20260064282-A

Abstract

The present invention relates to a composition for a semiconductor photoresist comprising an organometallic compound; an alcohol compound containing unsaturated bonds; and a solvent, and a method for forming a pattern using the same.

Inventors

변승환
임설희
오부근
장혜진
전종혁
백재열
최정민
신상훈
한미연

Assignees

삼성에스디아이 주식회사

Dates

Publication Date: 20260507
Application Date: 20241031

Claims (13)

Organometallic compounds; Alcohol compounds containing unsaturated bonds; and menstruum A composition for semiconductor photoresist comprising
In paragraph 1, A composition for a semiconductor photoresist, wherein the alcohol compound containing the above-mentioned unsaturated bond is represented by any one of the following Chemical Formulas 1 to 4: [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] In the above chemical formulas 1 to 4, R1 to R12 are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, or a combination thereof. L1 and L2 are each independently a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, or a combination thereof, and m1 to m12 are each independently integers of 0 or 1, and m1+m2+m3+m4 and m5+m6+m7+m8 are each independently one of integers 1 to 4, and m9+m10 and m11+m12 are each independently integers of 1 or 2.
In Paragraph 1, A composition for a semiconductor photoresist, wherein the above m1+m2+m3+m4 and m5+m6+m7+m8 are each independently integers of 1 or 2.
In Paragraph 1, A composition for a semiconductor photoresist in which the alcohol compound containing the above-mentioned unsaturated bond is one selected from the compounds listed in Group 1 below: [Group 1] .
In Paragraph 1, A semiconductor photoresist composition comprising an alcohol compound containing the above-mentioned unsaturated bond in an amount of 0.001 to 5 weight% based on 100 weight% of the semiconductor photoresist composition.
In Paragraph 1, A semiconductor photoresist composition in which the organometallic compound is included in an amount of 0.5% to 30% by weight based on 100% by weight of the semiconductor photoresist composition.
In Paragraph 1, A composition for a semiconductor photoresist further comprising an additive of a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, or a combination thereof.
In Paragraph 1, A composition for a semiconductor photoresist, wherein the above organometallic compound is an organotin compound comprising at least one of an organooxy group and an organocarbonyloxy group.
In paragraph 1, The above organometallic compound is a composition for a semiconductor photoresist represented by the following chemical formula 5: [Chemical Formula 5] In the above chemical formula 5, R 13 is selected from substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C3 to C20 cycloalkyl groups, substituted or unsubstituted C2 to C20 alkenyl groups, substituted or unsubstituted C2 to C20 alkynyl groups, substituted or unsubstituted C6 to C30 aryl groups, and substituted or unsubstituted C7 to C30 arylalkyl groups, and R 14 to R 16 are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, alkoxy and aryloxy (-OR b , where R b is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), a carboxyl group (-O(CO)R c , R c is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or An unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), an alkylamido or dialkylamido (-NR d R e , where R d and R e are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), an amidato (-NR f (COR g ), where R f and R g are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, Amidinato (-NR h C(NR i )R j , where R h , R i and R j are each independently hydrogen , a substituted or unsubstituted C1 to C20 alkyl group , a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof ) , alkylthio and aryltio (-SR k , where R k is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, A substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof) or a thiocarboxyl group (-S(CO)R l , R l is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), and At least one of R 14 to R 16 is an alkoxy and aryloxy (-OR b , where R b is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), a carboxyl group (-O(CO)R c , where R c is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), an alkylamido or dialkylamido (-NR d Re , where R d and Re e are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), amidato (-NR f (COR g ), where R f and R g are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), amidato (-NR g C(NR h )R i , where R h , R i and R j are each independently Hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), alkylthio and aryltio (-SR k , where R k is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof) and thiocarboxyl group (-S(CO)R l , R l is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or It is selected from unsubstituted C2 to C20 alkenyl groups, substituted or unsubstituted C2 to C20 alkinyl groups, substituted or unsubstituted C6 to C30 aryl groups, or combinations thereof.
In Paragraph 9, A composition for a semiconductor photoresist, wherein at least one of the above R 14 to R 16 is selected from alkoxy and aryloxy (-OR b , where R b is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), and a carboxyl group (-O(CO)R c , where R c is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof).
In Paragraph 10, The above R 13 is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group comprising one or more double or triple bonds, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C4 to C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof, and R b is a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, and A composition for a semiconductor photoresist in which R c is hydrogen, a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.
In Paragraph 1, The above organometallic compound is a composition for a semiconductor photoresist represented by the following chemical formula 6 or chemical formula 7: [Chemical Formula 6] R 17 z SnO (2-(z/2)-(x/2)) (OH) x In the above chemical formula 6, R 17 is a C1 to C31 hydrocarbyl group, where 0 < z ≤ 2 and 0 < (z+x) ≤ 4; [Chemical Formula 7] R 18 a Sn b X c Y d In the above chemical formula 7, R 18 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 aliphatic unsaturated organic group comprising one or more double or triple bonds, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof, and X is sulfur (S), selenium (Se), or tellurium (Te), and Y is -OR m or -OC(=O)R n , and The above R m is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, and R n is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, and The above a, b, c, and d are each independently integers from 1 to 20.
Step of forming an etching target film on a substrate; A step of forming a photoresist film by applying a composition for a semiconductor photoresist according to any one of claims 1 to 12 onto the above-mentioned etching target film; A step of patterning the above photoresist film to form a photoresist pattern; and A pattern forming method comprising the step of etching the etching target film using the above photoresist pattern as an etching mask.

Description

Semiconductor Photoresist Composition and Method of Forming Patterns Using the Composition The present invention relates to a composition for semiconductor photoresist and a method for forming a pattern using the same. EUV (Extreme Ultraviolet) lithography is attracting attention as one of the key technologies for manufacturing next-generation semiconductor devices. EUV lithography is a pattern formation technology that uses EUV light with a wavelength of 13.5 nm as an exposure light source. It has been demonstrated that EUV lithography can form extremely fine patterns (e.g., 20 nm or less) during the exposure process of semiconductor device manufacturing. The implementation of extreme ultraviolet (EUV) lithography requires the development of compatible photoresists capable of performing at spatial resolutions of 16 nm or less. Currently, traditional chemically amplified (CA) photoresists are striving to meet specifications for resolution, photospeed, feature roughness, and line edge roughness (LER) for next-generation devices. Intrinsic image blur caused by acid-catalyzed reactions occurring in these polymeric photoresists limits resolution at small feature sizes, a fact that has long been known in electron beam lithography. Although chemically amplified (CA) photoresists are designed for high sensitivity, they may face more difficulties under EUV exposure, partly because their typical elemental makeup lowers the absorbance of the photoresists at a wavelength of 13.5 nm, thereby reducing sensitivity. CA photoresists can also suffer from roughness issues at small feature sizes, and experiments have shown that line edge roughness (LER) increases as photospeed decreases, partly due to the nature of acid catalyst processes. Due to the defects and problems of CA photoresists, there is a demand in the semiconductor industry for new types of high-performance photoresists. Inorganic photosensitive compositions have been studied to overcome the disadvantages of the chemically amplified organic photosensitive compositions described above. Inorganic photosensitive compositions are primarily used for negative tone patterning that is resistant to removal by developer compositions due to chemical modification by non-chemical amplification mechanisms. Inorganic compositions contain inorganic elements that have a higher EUV absorption rate compared to hydrocarbons, so sensitivity can be ensured even by non-chemical amplification mechanisms, and they are known to be less sensitive to stochastic effects, resulting in lower line edge roughness and a smaller number of defects. Inorganic photoresists based on tungsten and peroxopolyacids of tungsten mixed with niobium, titanium, and/or tantalum have been reported for use in radiation-sensitive materials for patterning (US5061599; H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298-300, 1986). These materials were effective for patterning large features in bilayer configurations using deep UV, X-ray, and electron beam sources. More recently, impressive performance was shown when using cationic hafnium metal oxide sulfate (HfSOx) materials with a peroxo complexing agent to image 15 nm half-pitch (HP) by projection EUV lithography (US2011-0045406; 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). This system has demonstrated the best performance for non-CA photoresists and possesses a speed of light approaching the requirements for viable EUV photoresists. However, hafnium metal oxide sulfate materials with peroxo complexes have several practical drawbacks. First, these materials are coated in highly corrosive sulfuric acid/hydrogen peroxide mixtures, and shelf-life stability is poor. Second, as they are composite mixtures, structural modifications to improve performance are not easy. Third, they must be developed in extremely high concentrations, such as TMAH (tetramethylammonium hydroxide) solutions of about 25 wt%. Recently, active research has been conducted as it has become known that molecules containing tin exhibit excellent absorption of extreme ultraviolet light. In the case of organotin polymers, which are one such example, alkyl ligands dissociate due to light absorption or secondary electrons generated by it, and through cross-linking via oxo bonds with surrounding chains, negative tone patterning that cannot be removed by organic developers is possible. While such organotin polymers have demonstrated a dramatic improvement in sensitivity while maintaining resolution and line edge roughness, further improvement of the aforementioned patterning characteristics is required for commercialization. FIG. 1 is a cross-sectional view illustrating a method for forming a pattern using a composition for a semiconductor photoresist according to one embodiment. Hereinafter, embodiments of the present invention will be described in detail with re