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US-20260126724-A1 - SEMICONDUCTOR PHOTORESIST COMPOSITION AND METHOD OF FORMING PATTERNS USING THE COMPOSITION

US20260126724A1US 20260126724 A1US20260126724 A1US 20260126724A1US-20260126724-A1

Abstract

A semiconductor photoresist composition and a method of forming or providing patterns utilizing the semiconductor photoresist composition are disclosed. The semiconductor photoresist composition may include an organometallic compound represented by Chemical Formula 1 and a solvent.

Inventors

  • Sumin Jang
  • Soobin LIM
  • Joonhee Han
  • Yunju CHAE
  • Jimin Kim
  • Hyun Lee
  • Kyungmog KIM
  • Ahra CHO

Assignees

  • SAMSUNG SDI CO., LTD.

Dates

Publication Date
20260507
Application Date
20251104
Priority Date
20241106

Claims (20)

  1. 1 . A semiconductor photoresist composition, comprising: an organometallic compound represented by Chemical Formula 1; and a solvent: wherein, in Chemical Formula 1, R 1 is selected from among a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl 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 C2 to C30 heteroaryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C4 to C30 heteroarylalkyl group, and a substituted or unsubstituted C1 to C30 alkylcarbonyl group, X, Y, and Z are each independently selected from among a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl 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 C2 to C30 heteroaryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C4 to C30 heteroarylalkyl group, a substituted or unsubstituted C1 to C30 alkylcarbonyl group, —O-L a -R a , —S-L b -R b , and —O(CO)-L c -R c , at least one selected from among X, Y, and Z is —O-L a -R a , —S-L b -R b , or —O(CO)-L c -R c , L a , L b , and Le are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group, R a , R b , and R o are each independently —C(R 2 )═C(R 3 )(R 4 ) or —C≡C(R 5 ), R 2 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, R 3 and R 4 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, -L 1 -C═C(R 6 )(R 7 ), or -L 2 -C≡C(R 8 ), at least one selected from R 3 and R 4 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, -L 1 -C═C(R 6 )(R 7 ), or -L 2 -C≡C(R 8 ), R 5 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, -L 1 -C═C(R 6 )(R 7 ), or -L 2 -C≡C(R 8 ), L 1 and L 2 are a substituted or unsubstituted C1 to C10 alkylene group, and R 6 to R 8 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.
  2. 2 . The semiconductor photoresist composition as claimed in claim 1 , wherein: R a , R b , and R c are —C≡C(R 5 ), R 5 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, -L 1 -C═C(R 6 )(R 7 ), or -L 2 -C≡C(R 8 ), L 1 and L 2 are a substituted or unsubstituted C1 to C10 alkylene group, and R 6 to R 8 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.
  3. 3 . The semiconductor photoresist composition as claimed in claim 1 , wherein: X, Y, and Z are each independently —O-L a -R a , —S-L b -R b , or —O(CO)-L c -R c .
  4. 4 . The semiconductor photoresist composition as claimed in claim 3 , wherein: X, Y, and Z are the same each other.
  5. 5 . The semiconductor photoresist composition as claimed in claim 1 , wherein: R 1 is selected from among a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C20 heteroalkyl group, a substituted or unsubstituted C3 to C12 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C2 to C20 heteroaryl group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C4 to C20 heteroarylalkyl group, and a substituted or unsubstituted C1 to C20 alkylcarbonyl group.
  6. 6 . The semiconductor photoresist composition as claimed in claim 1 , wherein: R 1 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 butenyl group, a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propynyl group, a substituted or unsubstituted butynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted xylene group, or a substituted or unsubstituted benzyl group.
  7. 7 . The semiconductor photoresist composition as claimed in claim 1 , wherein: R 2 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, R 3 and R 4 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, -L 1 -C═C(R 6 )(R 7 ), or -L 2 -C≡C(R 8 ), at least one selected from R 3 and R 4 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, -L 1 -C═C(R 6 )(R 7 ), or -L 2 -C≡C(R 8 ), R 5 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, -L 1 -C═C(R 6 )(R 7 ), or -L 2 -C≡C(R 8 ), L 1 and L 2 are a substituted or unsubstituted C1 to C6 alkylene group, and R 6 to R 8 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.
  8. 8 . The semiconductor photoresist composition as claimed in claim 1 , wherein: R 2 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, R 3 and R 4 are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, -L 1 -C═C(R 6 )(R 7 ), or -L 2 -C≡C(R 8 ), at least one selected from R 3 and R 4 is a substituted or unsubstituted C1 to C10 alkyl group, -L 1 -C═C(R 6 )(R 7 ), or -L 2 -C≡C(R 8 ), R 5 is a substituted or unsubstituted C1 to C10 alkyl group, -L 1 -C═C(R 6 )(R 7 ), or -L 2 -C≡C(R 8 ), L 1 and L 2 are a substituted or unsubstituted C1 to C6 alkylene group, and R 6 to R 8 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.
  9. 9 . The semiconductor photoresist composition as claimed in claim 1 , wherein: the organometallic compound represented by Chemical Formula 1 is selected from among the compounds listed in Group 1:
  10. 10 . The semiconductor photoresist composition as claimed in claim 1 , wherein: the organometallic compound represented by Chemical Formula 1 is in an amount of 0.5 wt % to 30 wt % based on 100 wt % of the semiconductor photoresist composition.
  11. 11 . The semiconductor photoresist composition as claimed in claim 1 , further comprising other additives of a surfactant, a crosslinking agent, a leveling agent, an organic acid, a quencher, or a combination thereof.
  12. 12 . The semiconductor photoresist composition as claimed in claim 11 , wherein: the surfactant comprises at least one selected from among an alkyl benzene sulfonate salt, an alkyl pyridinium salt, polyethylene glycol, a quaternary ammonium salt, and a combination thereof.
  13. 13 . The semiconductor photoresist composition as claimed in claim 11 , wherein: the crosslinking agent comprises at least one selected from among a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, an acryl-based crosslinking agent, an epoxy-based crosslinking agent, a polymer-based crosslinking agent, and a combination thereof.
  14. 14 . The semiconductor photoresist composition as claimed in claim 11 , wherein: the organic acid comprises at least one selected from among p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, a fluorinated sulfonium salt, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, and a combination thereof.
  15. 15 . The semiconductor photoresist composition as claimed in claim 11 , wherein: the quencher comprises at least one selected from among diphenyl (p-tolyl) amine, methyl diphenyl amine, triphenyl amine, phenylenediamine, naphthylamine, diaminonaphthalene, and a combination thereof.
  16. 16 . The semiconductor photoresist composition as claimed in claim 1 , wherein: the solvent comprises at least one selected from among an aromatic compound, an alcohol, an ether, an ester, a ketone, and a combination thereof.
  17. 17 . A method of forming patterns, comprising: forming an etching-objective layer on a substrate; coating the semiconductor photoresist composition as claimed in claim 1 on the etching-objective layer to form a photoresist film; exposing and developing the photoresist film to form a photoresist pattern on the photoresist film; and etching the etching-objective layer utilizing the photoresist pattern as an etching mask.
  18. 18 . The method as claimed in claim 17 , wherein: the exposing and developing of the photoresist film is performed utilizing light having a wavelength in a range of 5 nm to 150 nm.
  19. 19 . The method as claimed in claim 17 , wherein: the photoresist pattern has a width in a range of 5 nm to 100 nm.
  20. 20 . The method as claimed in claim 17 , wherein: the photoresist pattern has a pitch having a half-pitch of less than or equal to 50 nm and a line width roughness of less than or equal to 5 nm.

Description

CROSS-REFERENCE TO RELATED APPLICATION The present application claims priority to and the benefit of Korean Patent Application No. 10-2024-0156547, filed on Nov. 6, 2024, in the Korean Intellectual Property Office, the entire disclosure 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 or providing patterns utilizing the semiconductor photoresist composition. 2. Description of the Related Art Extreme ultraviolet (EUV) lithography is paid attention to as one essential technology to manufacture a next generation semiconductor device. The EUV lithography is a pattern-forming technology using an EUV ray having a wavelength of 13.5 nm as an exposure light source. According to the EUV lithography, an extremely fine pattern (e.g., less than or equal to 20 nm) may be formed or provided in an exposure process during a manufacture of a semiconductor device. The extreme ultraviolet (EUV) lithography is realized through development of compatible photoresists which can be performed at a spatial resolution of less than or equal to 16 nm. Efforts to satisfy insufficient or unsuitable specifications of chemically amplified (CA) photoresists that are generally available, such as a resolution, a photospeed, and feature roughness (or also referred to as a line edge roughness or LER), for the next generation device are being made. An intrinsic image blurring due to an acid catalyzed reaction in the polymer-type or kind photoresists limits a resolution in small feature sizes, which has been experienced in electron beam (e-beam) lithography for a long time. The chemically amplified (CA) photoresists are designed for high sensitivity, but because their elemental makeups reduce light absorbance of the photoresists at a wavelength of 13.5 nm and thus decrease their sensitivity, the chemically amplified (CA) photoresists may partially have more difficulties under an EUV exposure. Also, the CA photoresists may have difficulties in the small feature sizes due to roughness issues, and line edge roughness (LER) of the CA photoresists experimentally turns out to be increased, as a photospeed is decreased partially due to an essence of acid catalyst processes. Accordingly, a novel high-performance photoresist is required or desired in a semiconductor industry because of these defects and problems of the CA photoresists. In order to overcome the drawbacks of the chemically amplified (CA) organic photosensitive composition, an inorganic photosensitive composition has been researched. The inorganic photosensitive composition is mainly or predominantly utilized for negative tone patterning having resistance against removal by a developer composition due to chemical modification through nonchemical amplification mechanism. The inorganic composition contains an inorganic element having a higher EUV absorption rate than hydrocarbon and thus may secure sensitivity through the nonchemical amplification mechanism and, in addition, is less sensitive about a stochastic effect and thus may have low line edge roughness and the small number of defects. Inorganic photoresists based on peroxopolyacids of tungsten mixed with tungsten, niobium, titanium, and/or tantalum are radiation-sensitive materials for patterning. These materials are effective or suitable to pattern large pitches for bilayer configuration or arrangement as far ultraviolet (deep UV), X-ray, and electron beam sources. Utilizing cationic hafnium metal oxide sulfate (HfSOx) materials along with a peroxo complexing agent to image a 15 nm half-pitch (HP) through projection EUV exposure exhibits the highest performance of a non-CA photoresist and has a practicable photospeed near to a requirement for an EUV photoresist. However, the hafnium metal oxide sulfate material having the peroxo complexing agent has a few practical drawbacks. First, these materials are coated in a mixture of corrosive sulfuric acid/hydrogen peroxide and have insufficient or unsuitable shelf-life stability. Second, a structural change of the materials for performance improvement or enhancement as a composite mixture is challenging. Third, development should be performed in a tetramethylammonium hydroxide (TMAH) solution at an extremely high concentration of 25 wt % and/or the like. Molecules including tin (Sn) have excellent or suitable absorption of extreme ultraviolet rays. As for an organotin polymer among them, alkyl ligands are dissociated by light absorption and/or secondary electrons produced thereby and are crosslinked with adjacent chains through oxo bonds and thus enable the negative tone patterning which may not be removed by an organic developer. This organotin polymer exhibits greatly or substantially improved or enhanced sensitivity as well as maintains a resolution and line edge roughness, but the patterning characteristics should be additionally improved or enhanced