US-20260126723-A1 - SEMICONDUCTOR PHOTORESIST COMPOSITION AND METHOD OF FORMING PATTERNS USING THE COMPOSITION

US20260126723A1US 20260126723 A1US20260126723 A1US 20260126723A1US-20260126723-A1

Abstract

A semiconductor photoresist composition and a method of forming patterns using the semiconductor photoresist composition are provided. The semiconductor photoresist composition including an organometallic compound, a carboxylic acid compound represented by Chemical Formula 1; and a solvent.

Inventors

Kyoungah OH
Seung-Wook Shin
Minhye KIM
Jihyun Yoon
Eunmi KANG
Jimin Kim

Assignees

SAMSUNG SDI CO., LTD.

Dates

Publication Date: 20260507
Application Date: 20251030
Priority Date: 20241101

Claims (13)

1 . A semiconductor photoresist composition, comprising an organometallic compound; a carboxylic acid compound represented by Chemical Formula 1; and a solvent: wherein, in 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 alkynylene group, and Z 1 to Z 3 are each independently hydrogen, a hydroxy 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, provided that at least one selected from among L and Z 1 to Z 3 comprises a nitro group.
2 . The semiconductor photoresist composition as claimed in claim 1 , wherein L is a single bond or a substituted or unsubstituted C1 to C10 alkylene group.
3 . The semiconductor photoresist composition as claimed in claim 1 , wherein Z 1 to Z 3 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, provided that at least one selected from among Z 1 to Z 3 is a nitro group.
4 . The semiconductor photoresist composition as claimed in claim 1 , wherein the carboxylic acid compound represented by Chemical Formula 1 is in an amount of 0.01 wt % to 5 wt % based on a total weight of 100 wt % of the semiconductor photoresist composition.
5 . The semiconductor photoresist composition as claimed in claim 1 , wherein the carboxylic acid compound represented by Chemical Formula 1 is selected from among compounds listed in Group 1:
6 . The semiconductor photoresist composition as claimed in claim 1 , wherein the semiconductor photoresist composition further comprises one or more additives selected from among a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, and a combination thereof.
7 . The semiconductor photoresist composition as claimed in claim 1 , wherein the organometallic compound comprises an organotin compound comprising at least one of an organooxy group or an organocarbonyloxy group.
8 . The semiconductor photoresist composition as claimed in claim 1 , wherein the organometallic compound is represented by Chemical Formula 2: and wherein, in Chemical Formula 2, R 1 is selected from among 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, and a substituted or unsubstituted C7 to C30 arylalkyl group, R 2 to R 4 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, an alkoxy or aryloxy group (—OR b , wherein 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 , wherein 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 group (—NR d R e , wherein 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 group (—NR f (COR g ), wherein 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), an amidinato group (—NR h C(NR i )R i , wherein R h , R i , and R i 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 alkylthio or arylthio group (—SR k , wherein 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 I , wherein R I 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 selected from among R 2 to R 4 is selected from among an alkoxy or aryloxy group (—OR b , wherein 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 , wherein 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 group (—NR d R e , wherein 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 group (—NR f (COR g ), wherein 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), an amidinato group (—NR h C(NR i )R i , wherein R h , R i , and R i 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 alkylthio or arylthio group (—SR k , wherein 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 a thiocarboxyl group (—S(CO)R I , wherein R I 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).
9 . The semiconductor photoresist composition as claimed in claim 8 , wherein at least one selected from among R 2 to R 4 is selected from among an alkoxy or aryloxy group (—OR b , wherein 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 , wherein 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).
10 . The semiconductor photoresist composition as claimed in claim 9 , wherein R 1 is selected from among 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, and a substituted or unsubstituted C7 to C20 arylalkyl group, 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 R c is a 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 combination thereof.
11 . The semiconductor photoresist composition as claimed in claim 1 , wherein the organometallic compound is represented by Chemical Formula 3 or Chemical Formula 4: in Chemical Formula 3, R 5 being a C1 to C31 hydrocarbyl group, 0<z≤2, and 0< (z+x)≤4; and in Chemical Formula 4, R 6 being 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 bonds or triple bonds, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a carbonyl group, ethylene oxide group, propylene oxide group, or a combination thereof, X being sulfur, selenium, or tellurium, Y being —OR m or —OC(═O)R n , wherein 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 a, b, c, and d being each independently an integer of 1 to 20.
12 . A method, comprising forming an etching-objective layer on a substrate; coating the semiconductor photoresist composition of claim 1 on the etching-objective layer to form a photoresist film; patterning the photoresist film to form a photoresist pattern; and etching the etching-objective layer utilizing the photoresist pattern as an etching mask, wherein the method is a method of forming patterns.
13 . A system, comprising means for forming an etching-objective layer on a substrate; means for coating the semiconductor photoresist composition of claim 1 on the etching-objective layer to form a photoresist film; means for patterning the photoresist film to form a photoresist pattern; and means for etching the etching-objective layer utilizing the photoresist pattern as an etching mask, wherein the system is a system of forming patterns.

Description

CROSS-REFERENCE TO RELATED APPLICATION The present application claims priority to and the benefit of Korean Patent Application No. 10-2024-0153667, filed on Nov. 1, 2024, in the Korean Intellectual Property Office, the entire content of which is incorporated herein by reference. BACKGROUND 1. Field One or more embodiments of the present disclosure relate to a semiconductor photoresist composition and a method of forming patterns using the same. 2. Description of the Related Art Extreme ultraviolet (EUV) lithography has emerged as an important technology for manufacturing next-generation semiconductor devices, such as advanced semiconductor chips (e.g., next generation semiconductor chips). EUV lithography utilizes EUV radiation with a wavelength of 13.5 nm as an exposure light source, enabling the formation of extremely fine patterns, for example, patterns having critical dimensions of 20 nm or less. Achieving high-resolution patterning with EUV lithography requires the development of compatible photoresists capable of sub-16 nm resolution. However, chemically amplified (CA) photoresists currently face limitations in resolution, photospeed, and line edge roughness (LER), which hinder their performance in advanced lithographic processes. In CA photoresists, acid-catalyzed reactions may cause image blurring, particularly at small feature sizes, a limitation also observed in electron beam lithography. Although CA photoresists are designed for high sensitivity, their typical elemental composition results in low absorbance at 13.5 nm, thereby reducing sensitivity under EUV exposure. Additionally, CA photoresists often exhibit increased LER as photospeed decreases, due in part to the stochastic nature of acid diffusion and reaction. These limitations create the need or desire for novel, high-performance photoresist materials suitable for EUV lithography. In response, research has turned to inorganic photoresist compositions, which are primarily used for negative tone patterning. These compositions undergo chemical modification through non-chemically amplified mechanisms, providing resistance to developer solutions. Inorganic photoresists typically contain elements with higher EUV absorption than hydrocarbons, offering improved sensitivity, reduced stochastic effects, and lower LER. Inorganic photoresists based on peroxopolyacids of tungsten, optionally mixed with elements such as niobium, titanium, and/or tantalum, have been explored as radiation sensitive materials for patterning. These materials have demonstrated efficacy in patterning large-pitch features using bilayer configurations and various radiation sources, including deep UV, X-ray, and electron beam. For example, cationic hafnium metal oxide sulfate (HfSOx) materials, when combined with a peroxo complexing agent, have enabled imaging of 15 nm half-pitch features via EUV projection exposure. While this system offers high performance and acceptable photospeed, it suffers from practical drawbacks: (i) the coating process involves corrosive sulfuric acid/hydrogen peroxide mixtures, leading to poor shelf-life stability; (ii) structural modifications for performance enhancement are difficult; and (iii) development requires highly concentrated tetramethylammonium hydroxide (TMAH) solutions (e.g., 25 wt %). To address these issues and challenges, recent efforts have focused on tin-containing molecules with strong EUV absorption. Among these, organotin polymers have shown promise. Upon EUV exposure, alkyl ligands dissociate and form oxo bonds with adjacent chains, enabling negative tone patterning resistant to organic developers. Although these organotin polymers exhibit improved sensitivity, resolution, and LER, further enhancements are needed or desired to meet commercial performance requirements. SUMMARY One or more aspects of embodiments of the present disclosure are directed toward a semiconductor photoresist composition that has excellent or suitable resolution characteristics and pattern adhesive force by reducing the influence of variables during pattern formation and thus improves CD (critical dimension) stability. One or more aspects of embodiments of the present disclosure are directed toward a method of forming patterns using the semiconductor photoresist composition. Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments of the disclosure. According to one or more embodiments of the present disclosure, a semiconductor photoresist composition includes an organometallic compound, a carboxylic acid compound represented by Chemical Formula 1, and a solvent: In Chemical Formula 1, L may be 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 alkynylene group, and Z1 to Z3 may each independently be hyd