KR-20260065356-A - SEMICONDUCTOR PHOTORESIST COMPOSITION AND METHOD OF FORMING PATTERNS USING THE COMPOSITION

KR20260065356AKR 20260065356 AKR20260065356 AKR 20260065356AKR-20260065356-A

Abstract

The present invention relates to a composition for a semiconductor photoresist comprising an organometallic compound; a carboxylic acid compound represented by the following chemical formula 1; and a solvent, and a method for forming a pattern using the same. [Chemical Formula 1] The definition of the above chemical formula 1 is as stated in the specification.

Inventors

오경아
신승욱
김민혜
윤지현
강은미
김지민

Assignees

삼성에스디아이 주식회사

Dates

Publication Date: 20260508
Application Date: 20241101

Claims (12)

Organometallic compounds; A carboxylic acid compound represented by the following chemical formula 1; and Composition for semiconductor photoresist comprising a solvent: [Chemical Formula 1] In the above chemical formula 1, L is a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkenylene group, or a substituted or unsubstituted C2 to C10 alkylene group, and Z1 to Z3 are each independently hydrogen, a hydroxyl group, a halogen, a cyano group, a cyano-containing group, an ammonium group, an amide group, a nitro group, a carboxyl group, an ester group, a sulfone group, a sulfonate group, 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, or a combination thereof, The above L and Z 1 to Z 3 include at least one nitro group.
A composition for a semiconductor photoresist according to claim 1, wherein L of Formula 1 is a single bond, or a substituted or unsubstituted C1 to C10 alkylene group.
A composition for a photoresist according to claim 1, wherein Z1 to Z3 of the above formula 1 are each independently hydrogen, a cyano group, an ammonium group, an amide group, a nitro group, a carboxyl group, an ester group, or a combination thereof, wherein at least one of Z1 to Z3 is a nitro group.
A semiconductor photoresist composition according to claim 1, wherein the carboxylic acid compound represented by the above chemical formula 1 is included in an amount of 0.01% to 5% by weight based on 100% by weight of the semiconductor photoresist composition.
A composition for a semiconductor photoresist according to claim 1, wherein the carboxylic acid compound represented by the above chemical formula 1 is one selected from the compounds listed in Group 1 below: [Group 1]
A composition for a semiconductor photoresist according to claim 1, wherein the composition further comprises an additive of a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, or a combination thereof.
A composition for a semiconductor photoresist according to claim 1, wherein the organometallic compound is an organotin compound comprising at least one of an organooxy group and an organocarbonyloxy group.
In claim 1, the composition for a semiconductor photoresist, wherein the organometallic compound is represented by the following chemical formula 2: [Chemical Formula 2] In the above chemical formula 2, R1 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 R2 to R4 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 , where R c is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted A C3 to C20 cycloalkyl group, substituted or unsubstituted C2 to C20 alkenyl group, substituted or unsubstituted C2 to C20 alkynyl group, substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), 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), 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 groups, substituted or unsubstituted C2 to C20 alkynyl groups, substituted or unsubstituted C6 to C30 aryl groups, or a combination thereof), 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 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 (1-20 alkynyl group, substituted or unsubstituted C6-C30 aryl group, or a combination thereof) or thiocarboxyl group (-S(CO)R l , R l is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), and At least one of R2 to R4 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 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 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 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, or a combination thereof), alkylthio and aryltio (-SR k , where R k is a substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C2 to C20 alkenyl group, substituted or unsubstituted C2 to C20 alkynyl group, substituted or unsubstituted C6 to C30 aryl group, or a combination thereof) and thiocarboxyl groups (-S(CO)R l , where R l is hydrogen, substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C3 to C20 cycloalkyl groups, substituted or unsubstituted C2 to C20 It is selected from an alkenyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.
A composition for a semiconductor photoresist according to claim 8, wherein at least one of R2 to R4 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 claim 9, the R1 is selected from substituted or unsubstituted C1 to C8 alkyl groups, substituted or unsubstituted C3 to C8 cycloalkyl groups, substituted or unsubstituted C2 to C8 alkenyl groups, substituted or unsubstituted C2 to C8 alkynyl groups, substituted or unsubstituted C6 to C20 aryl groups, and substituted or unsubstituted C7 to C20 arylalkyl groups, 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.
A composition for a semiconductor photoresist according to claim 1, wherein the organometallic compound is represented by the following chemical formula 3 or chemical formula 4: [Chemical Formula 3] R 5 z SnO (2-(z/2)-(x/2)) (OH) x In the above chemical formula 3, R 5 is a C1 to C31 hydrocarbyl group, where 0 < z ≤ 2 and 0 < (z+x) ≤ 4; [Chemical Formula 4] R 6 a Sn b X c Y d In the above chemical formula 4, R6 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 11 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