KR-20260067884-A - SEMICONDUCTOR PHOTORESIST COMPOSITION AND METHOD OF FORMING PATTERNS USING THE COMPOSITION

KR20260067884AKR 20260067884 AKR20260067884 AKR 20260067884AKR-20260067884-A

Abstract

The present invention relates to a composition for a semiconductor photoresist comprising an organometallic compound represented by Chemical Formula 1 and a solvent, and a method for forming a pattern using the same. Detailed information regarding Chemical Formula 1 is as described in the specification.

Inventors

장수민
임수빈
한준희
채윤주
김지민
이현
김경목
조아라

Assignees

삼성에스디아이 주식회사

Dates

Publication Date: 20260513
Application Date: 20241106

Claims (14)

An organometallic compound represented by the following chemical formula 1; and menstruum A composition for semiconductor photoresist comprising: [Chemical Formula 1] In the above chemical formula 1, R1 is selected from substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C2 to C30 heteroalkyl groups, substituted or unsubstituted C3 to C20 cycloalkyl groups, substituted or unsubstituted C2 to C30 heterocycloalkyl 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, substituted or unsubstituted C2 to C30 heteroaryl groups, substituted or unsubstituted C7 to C30 arylalkyl groups, substituted or unsubstituted C4 to C30 heteroarylalkyl groups, and substituted or unsubstituted C1 to C30 alkylcarbonyl groups, and X, Y, and Z are each independently selected from substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C2 to C30 heteroalkyl groups, substituted or unsubstituted C3 to C20 cycloalkyl groups, substituted or unsubstituted C2 to C30 heterocycloalkyl 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, substituted or unsubstituted C2 to C30 heteroaryl groups, substituted or unsubstituted C7 to C30 arylalkyl groups, substituted or unsubstituted C4 to C30 heteroarylalkyl groups, substituted or unsubstituted C1 to C30 alkylcarbonyl groups, -OL a -R a , -SL b -R b and -O(CO)-L c -R c , and At least one of X, Y and Z is -OL a -R a , -SL b -R b or -O(CO)-L c -R c , and The above L a , L b , and L c are each independently single-bonded, substituted, or unsubstituted C1 to C10 alkylene groups, and The above R a , R b , and R c are each independently -C(R 2 )=C(R 3 )(R 4 ) or -C≡C(R 5 ), and R2 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, or a substituted or unsubstituted C6 to C30 aryl group, and R3 and R4 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 C6 to C30 aryl group, -L1 -C=C( R6 )( R7 ), or -L2- C≡C( R8 ), and At least one of R3 and R4 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, -L1 -C=C( R6 )( R7 ), or -L2 -C≡C( R8 ), and R5 is each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, -L1 -C=C( R6 )( R7 ), or -L2- C≡C( R8 ), and L1 and L2 are each independently substituted or unsubstituted C1 to C10 alkylene groups, and R6 to R8 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, or a substituted or unsubstituted C6 to C30 aryl group.
In Paragraph 1, The above R a , R b , and R c are each independently -C≡C(R 5 ), and R5 is each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, -L1 -C=C( R6 )( R7 ), or -L2- C≡C( R8 ), and L1 and L2 are each independently substituted or unsubstituted C1 to C10 alkylene groups, and A composition for a semiconductor photoresist, wherein R6 to R8 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, or a substituted or unsubstituted C6 to C30 aryl group.
In Paragraph 1, A composition for a semiconductor photoresist, wherein X, Y, and Z are each independently -OL a -R a , -SL b -R b , or -O(CO)-L c -R c .
In Paragraph 3, A composition for a semiconductor photoresist, wherein X, Y, and Z are identical to each other.
In Paragraph 1, A composition for a semiconductor photoresist, wherein the above R1 is selected from substituted or unsubstituted C1 to C10 alkyl groups, substituted or unsubstituted C2 to C20 heteroalkyl groups, substituted or unsubstituted C3 to C12 cycloalkyl groups, substituted or unsubstituted C2 to C20 heterocycloalkyl groups, substituted or unsubstituted C2 to C10 alkenyl groups, substituted or unsubstituted C2 to C10 alkynyl groups, substituted or unsubstituted C6 to C20 aryl groups, substituted or unsubstituted C2 to C20 heteroaryl groups, substituted or unsubstituted C7 to C20 arylalkyl groups, substituted or unsubstituted C4 to C20 heteroarylalkyl groups, and substituted or unsubstituted C1 to C20 alkylcarbonyl groups.
In Paragraph 1, The above R1 is a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted tert-pentyl group, a substituted or unsubstituted 1-methylpropyl group, a substituted or unsubstituted 1,1-dimethylpropyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted ethenyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butanyl group, a substituted or unsubstituted propinyl group, a substituted or unsubstituted butanyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted A composition for semiconductor photoresist comprising a xylene group, a substituted or unsubstituted benzyl group, or a combination thereof.
In Paragraph 1, The above R2 is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, or a substituted or unsubstituted C6 to C20 aryl group, and R3 and R4 are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, -L1 -C=C( R6 )( R7 ), or -L2- C≡C( R8 ), and At least one of R3 and R4 is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, -L1 -C=C( R6 )( R7 ), or -L2 -C≡C( R8 ), and R5 is each independently a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, -L1 -C=C( R6 )( R7 ), or -L2- C≡C( R8 ), and L1 and L2 are each independently substituted or unsubstituted C1 to C6 alkylene groups, and A composition for a semiconductor photoresist, wherein R6 to R8 are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, or a substituted or unsubstituted C6 to C20 aryl group.
In Paragraph 1, The above R2 is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, or a substituted or unsubstituted C2 to C10 alkynyl group, and R3 and R4 are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, -L1 -C=C( R6 )( R7 ), or -L2- C≡C( R8 ), and At least one of R3 and R4 is a substituted or unsubstituted C1 to C10 alkyl group, -L1 -C=C( R6 )( R7 ), or -L2- C≡C( R8 ), and R5 is each independently a substituted or unsubstituted C1 to C10 alkyl group, -L1 -C=C( R6 )( R7 ), or -L2- C≡C( R8 ), and L1 and L2 are each independently substituted or unsubstituted C1 to C6 alkylene groups, and A composition for a semiconductor photoresist, wherein R6 to R8 are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, or a substituted or unsubstituted C2 to C10 alkynyl group.
In Paragraph 1, A composition for a semiconductor photoresist, wherein the organometallic compound represented by the above chemical formula 1 is one selected from the compounds listed in Group 1 below: [Group 1] .
In Paragraph 1, A semiconductor photoresist composition comprising an organometallic compound represented by the above chemical formula 1 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 a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, or other additives in combination thereof.
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 11 onto the above-mentioned etching target film; A step of exposing and developing the above photoresist film to form a photoresist film having 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.
In Paragraph 12, The step of forming the above photoresist pattern is a pattern forming method using light with a wavelength of 5 nm to 150 nm.
In Paragraph 1, The above photoresist pattern is a pattern forming method having a width of 5 nm to 100 nm.

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