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CN-122018232-A - Semiconductor photoresist composition and method of forming pattern using the same

CN122018232ACN 122018232 ACN122018232 ACN 122018232ACN-122018232-A

Abstract

Disclosed are a semiconductor photoresist composition including an organometallic compound, a pyrrole-based compound including pyrrole, a pyrrole derivative, or a combination thereof, and a solvent, and a method of forming or providing a pattern using the same.

Inventors

  • JIANG XIYI
  • JIN MINHUI

Assignees

  • 三星SDI株式会社

Dates

Publication Date
20260512
Application Date
20251112
Priority Date
20241112

Claims (20)

  1. 1. A semiconductor photoresist composition comprising: an organometallic compound; Pyrrole compounds comprising pyrrole, pyrrole derivatives or combinations thereof, and And (3) a solvent.
  2. 2. The semiconductor photoresist composition of claim 1, wherein the pyrrole compound is represented by chemical formula 1: Chemical formula 1 Wherein, in the chemical formula 1, L 1 to L 5 are each independently a single bond, carbonyl, substituted or unsubstituted C1 to C10 alkylene, substituted or unsubstituted C2 to C10 alkenylene, substituted or unsubstituted C3 to C10 cycloalkylene, substituted or unsubstituted C6 to C20 arylene, or a combination thereof, and R 1 to R 5 are each independently hydrogen, deuterium, hydroxy, halogen, cyano, amino, aldehyde, acetyl, carboxyl, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.
  3. 3. The semiconductor photoresist composition of claim 2, wherein L 1 to L 5 of chemical formula 1 are each independently a single bond, a carbonyl group, a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof.
  4. 4. The semiconductor photoresist composition of claim 2, wherein R 1 to R 5 of chemical formula 1 are each independently hydrogen, hydroxy, halogen, cyano, amino, aldehyde, acetyl, carboxyl, substituted or unsubstituted C1 to C5 alkyl, or a combination thereof.
  5. 5. The semiconductor photoresist composition of claim 1, wherein the pyrrole compound is at least one selected from group 1: Group 1 。
  6. 6. The semiconductor photoresist composition of claim 1, wherein the pyrrole compound is present in an amount of 0.01 wt% to 5 wt% based on 100 wt% of the semiconductor photoresist composition.
  7. 7. The semiconductor photoresist composition of claim 1, wherein the semiconductor photoresist composition further comprises an additive comprising a surfactant, a crosslinker, a leveling agent, an organic acid, a quencher, or a combination thereof.
  8. 8. The semiconductor photoresist composition of claim 1, wherein the organometallic compound comprises an organotin compound comprising at least one selected from the group consisting of an organooxy group and an organocarbonyloxy group.
  9. 9. The semiconductor photoresist composition of claim 1, wherein the organometallic compound is represented by chemical formula 2: Chemical formula 2 Wherein, in the chemical formula 2, R 6 is selected from the group consisting of substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and substituted or unsubstituted C7 to C30 aralkyl, R 7 to R 9 are each independently of the other substituted OR unsubstituted C1 to C20 alkyl, substituted OR unsubstituted C3 to C20 cycloalkyl, substituted OR unsubstituted C2 to C20 alkenyl, substituted OR unsubstituted C2 to C20 alkynyl, substituted OR unsubstituted C6 to C30 aryl, substituted OR unsubstituted C7 to C30 aralkyl, alkoxy OR aryloxy represented by-OR b , wherein R b is substituted OR unsubstituted C1 to C20 alkyl, Substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, a carboxyl or acyloxy group represented by-O (CO) R c wherein R c is hydrogen, substituted or unsubstituted C1 to C20 alkyl, Substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, an alkylamide or dialkylamide group represented by-NR d R e , wherein R d and R e are each independently hydrogen, Substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, an amide group represented by-NR f (COR g ), wherein R f and R g are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, amidino represented by-NR h C(NR i )R j wherein R h 、R i and R j are each independently hydrogen, Substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, alkylthio and/or arylthio represented by-SR k wherein R k is substituted or unsubstituted C1 to C20 alkyl, Substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, or thiocarbonyl represented by-S (CO) R l wherein R l is hydrogen, substituted or unsubstituted C1 to C20 alkyl, A substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and At least one selected from R 7 to R 9 is selected from alkoxy and aryloxy represented by-OR b , wherein R b is substituted OR unsubstituted C1 to C20 alkyl, Substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, a carboxyl or acyloxy group represented by-O (CO) R c wherein R c is hydrogen, substituted or unsubstituted C1 to C20 alkyl, Substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, alkylamide and dialkylamide groups represented by-NR d R e , wherein R d and R e are each independently hydrogen, Substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, an amide group represented by-NR f (COR g ), wherein R f and R g are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, amidino represented by-NR h C(NR i )R j wherein R h 、R i and R j are each independently hydrogen, Substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, alkylthio and/or arylthio represented by-SR k wherein R k is substituted or unsubstituted C1 to C20 alkyl, Substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and thiocarbonyl represented by-S (CO) R l , wherein R l is hydrogen, substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof.
  10. 10. The semiconductor photoresist composition of claim 9, wherein at least one selected from the group consisting of R 7 to R 9 is selected from the group consisting of alkoxy and aryloxy represented by-OR b , wherein R b is a substituted OR unsubstituted C1 to C20 alkyl, a substituted OR unsubstituted C3 to C20 cycloalkyl, a substituted OR unsubstituted C2 to C20 alkenyl, a substituted OR unsubstituted C2 to C20 alkynyl, a substituted OR unsubstituted C6 to C30 aryl, OR a combination thereof, and carboxy OR acyloxy represented by-O (CO) R c , wherein R c is hydrogen, a substituted OR unsubstituted C1 to C20 alkyl, a substituted OR unsubstituted C3 to C20 cycloalkyl, a substituted OR unsubstituted C2 to C20 alkenyl, a substituted OR unsubstituted C2 to C20 alkynyl, a substituted OR unsubstituted C6 to C30 aryl, OR a combination thereof.
  11. 11. The semiconductor photoresist composition according to claim 10, where R 6 is selected from the group consisting of substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 alkenyl, substituted or unsubstituted C2 to C8 alkynyl, substituted or unsubstituted C6 to C20 aryl, and substituted or unsubstituted C7 to C20 aralkyl, R b is substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 alkenyl, substituted or unsubstituted C2 to C8 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof, and R c is hydrogen, substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 alkenyl, substituted or unsubstituted C2 to C8 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.
  12. 12. The semiconductor photoresist composition of claim 1, wherein the organometallic compound is represented by chemical formula 3 or chemical formula 4: Chemical formula 3 R 10 z SnO (2-(z/2)-(x/2)) (OH) x Wherein, in the chemical formula 3, R 10 is a C1 to C31 hydrocarbon group, 0 < z≤2, and 0 < (z+x). Ltoreq.4; Chemical formula 4 R 11 a Sn b X c Y d Wherein, in the chemical formula 4, R 11 is a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 aliphatically unsaturated organic group comprising one or more double or triple bonds, a substituted or unsubstituted C6 to C30 aryl, a substituted or unsubstituted C4 to C30 heteroaryl, a carbonyl, an oxirane, an oxetanyl, or a combination thereof, X is sulfur (S), selenium (Se) or tellurium (Te), Y is-OR m OR-OC (=O) R n , Wherein R m is substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and R n is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and A. b, c and d are each independently integers from 1 to 20.
  13. 13. A method of forming a pattern, comprising: providing an etch target layer on a substrate; Coating the semiconductor photoresist composition of claim 1 on the etching target layer to form a photoresist film; patterning the photoresist film to form a photoresist pattern, and The etching target layer is etched using the photoresist pattern as an etching mask.
  14. 14. The method of forming a pattern of claim 13, wherein: the semiconductor photoresist composition further comprises at least one selected from the group consisting of surfactants, dispersants, moisture absorbents, coupling agents, and combinations thereof.
  15. 15. The method of forming a pattern of claim 14, wherein: The surfactant comprises at least one selected from the group consisting of sulfate salts, sulfonate salts, phosphate esters, soaps, amine salts, quaternary ammonium salts, polyethylene glycol, alkylphenol ethylene oxide adducts, polyols, nitrogen-containing vinyl polymers, and combinations thereof.
  16. 16. The method of forming a pattern of claim 14, wherein: the surfactant is present in an amount of 0.001 wt% to 3 wt% based on 100 wt% of the semiconductor photoresist composition.
  17. 17. The method of forming a pattern of claim 14, wherein: the dispersant comprises at least one selected from the group consisting of epoxy resin, polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, glucose, sodium lauryl sulfate, sodium citrate, oleic acid, linoleic acid, and combinations thereof.
  18. 18. The method of claim 13, wherein the method is performed in an atmosphere comprising nitrogen oxides.
  19. 19. A photoresist pattern formed according to the method of claim 13, wherein the photoresist pattern has a width of 5 nm to 100 nm.
  20. 20. A photoresist pattern formed according to the method of claim 13, wherein the photoresist pattern is formed in an atmosphere comprising oxynitride.

Description

Semiconductor photoresist composition and method of forming pattern using the same Cross reference to related applications The present application claims priority and benefit from korean patent application No. 10-2024-0160355, filed on 11 months 12 of 2024, the entire contents of which are incorporated herein by reference. Technical Field Embodiments of the present disclosure relate to semiconductor photoresist compositions and methods of forming patterns using the same. Background Extreme ultraviolet (extreme ultraviolet, EUV) lithography is attracting attention as a technique for manufacturing next-generation semiconductor devices. EUV lithography is a patterning technique using EUV radiation having a wavelength of 13.5 nm as an exposure light source. According to EUV lithography, extremely fine patterns (e.g., less than or equal to 20 nm) can be formed or provided in an exposure process during the fabrication of semiconductor devices. Extreme Ultraviolet (EUV) lithography is achieved by developing compatible photoresists that can be processed at spatial resolutions less than or equal to 16 nanometers. Efforts have been made to meet the insufficient or inadequate specifications of next generation devices for chemically amplified (CHEMICALLY AMPLIFIED, CA) photoresists, such as resolution, photospeed, and feature roughness (also known as line edge roughness (line edge roughness) or LER). Intrinsic image blur due to acid catalyzed reactions in polymeric or generic photoresists limits resolution in small feature sizes, which has long been experienced in electron beam (e-beam) lithography. Chemically Amplified (CA) photoresists are designed to have high sensitivity, but because their elemental composition reduces the light absorption of the photoresist at 13.5 nm wavelength, thereby reducing their sensitivity, chemically Amplified (CA) photoresists may be partially more difficult with EUV exposure. Furthermore, CA photoresists may have difficulty in small feature sizes due to roughness issues, and Line Edge Roughness (LER) experiments of CA photoresists demonstrate that they increase because the photospeed is reduced in part due to the nature of the acid catalyst process. Thus, due to these drawbacks and problems with CA photoresists, the semiconductor industry needs or desires a new type of high performance photoresist. In order to overcome the disadvantages of Chemically Amplified (CA) organic photosensitive compositions, inorganic photosensitive compositions have been studied. Inorganic photosensitive compositions are used primarily or predominantly for negative tone (negative tone) patterning with the ability to resist removal of developer compositions by chemical modification of non-chemical amplification mechanisms. The inorganic composition contains an inorganic element having a higher EUV absorptivity than hydrocarbon, and thus can ensure sensitivity by a non-chemical amplification mechanism, and furthermore, is less sensitive to random effects, and thus can have low line edge roughness and a smaller number of defects. Inorganic photoresists based on peroxy polyacids of tungsten mixed with tungsten, niobium, titanium and/or tantalum are radiation-sensitive materials for patterning. These materials are effective or suitable for large pitch patterning of bilayer configurations in terms of extreme ultraviolet (deep UV) light, X-ray, and electron beam sources. Imaging 15 nanometer Half Pitch (HP) with a cationic hafnium metal oxide sulfate (HfSOx) material together with a peroxycomplexing agent by projection EUV exposure provides impressive performance. The system exhibits the highest performance of non-CA photoresists and has practical photospeed approaching EUV photoresist requirements. However, hafnium metal oxide sulfate materials with peroxycomplexing agents have some practical drawbacks. First, these materials are coated in a corrosive sulfuric acid/hydrogen peroxide mixture and have inadequate or inadequate shelf life stability. Structural changes to improve the performance as a composite mixture are not easy. Third, development should be performed in extremely high concentrations of 25 wt% tetramethyl ammonium hydroxide (tetramethylammonium hydroxide, TMAH) solution and/or the like. Molecules including tin (Sn) have excellent or suitable extreme ultraviolet absorption. For organotin polymers therein, the alkyl ligands are dissociated by light absorption and/or secondary electrons generated therefrom, and cross-linked with adjacent chains by oxo bonds (oxo bond), thereby achieving negative tone (negative tone) patterning which cannot be removed by organic developer. While such organotin polymers exhibit greatly or substantially improved sensitivity and retention resolution and line edge roughness, patterning characteristics should be additionally improved or enhanced for commercial availability. Disclosure of Invention Some exemplary embodiments of the present disclosure provide a semiconductor pho