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CN-121995696-A - Semiconductor photoresist composition and method of forming pattern using the same

CN121995696ACN 121995696 ACN121995696 ACN 121995696ACN-121995696-A

Abstract

A semiconductor photoresist composition and a method of forming or providing a pattern using the same are disclosed. The semiconductor photoresist composition may include an organometallic compound represented by chemical formula 1, and a solvent.

Inventors

  • ZHANG SHUIMIN
  • LIN XIUBIN
  • HAN JUNXI
  • Cai Runzhu
  • JIN ZHIMIN
  • LI XIAN
  • JIN JINGMU
  • Cao Yaluo

Assignees

  • 三星SDI株式会社

Dates

Publication Date
20260508
Application Date
20251105
Priority Date
20241106

Claims (14)

  1. 1. A semiconductor photoresist composition comprising: An organometallic compound represented by chemical formula 1, and Solvent: Chemical formula 1 Wherein in the chemical formula 1, R 1 is selected from the group consisting of substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C30 heteroalkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heteroaryl, substituted or unsubstituted C7 to C30 aralkyl, substituted or unsubstituted C4 to C30 heteroaralkyl, and substituted or unsubstituted C1 to C30 alkylcarbonyl, X, Y and Z are each independently selected from the group consisting of substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C30 heteroalkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heteroaryl, substituted or unsubstituted C7 to C30 aralkyl, substituted or unsubstituted C4 to C30 heteroaralkyl, substituted or unsubstituted C1 to C30 alkylcarbonyl, -O-L a -R a 、-S-L b -R b , and-O (CO) -L c -R c , At least one selected from 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 L c are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group, R a 、R b and R c are each independently-C (R 2 )=C(R 3 )(R 4 ) or-C.ident.C (R 5 ), R 2 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, or substituted or unsubstituted C6 to C30 aryl, R 3 and R 4 are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, -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, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C6 to C30 aryl, -L 1 -C=C(R 6 )(R 7 ), or-L 2 -C≡C(R 8 ), R 5 is substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, -L 1 -C=C(R 6 )(R 7 ), or-L 2 -C≡C(R 8 ), L 1 and L 2 are substituted or unsubstituted C1 to C10 alkylene, and R 6 to R 8 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, or substituted or unsubstituted C6 to C30 aryl.
  2. 2. The semiconductor photoresist composition of claim 1, wherein: R a 、R b and R c are-C.ident.C (R 5 ), R 5 is substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, -L 1 -C=C(R 6 )(R 7 ), or-L 2 -C≡C(R 8 ), L 1 and L 2 are substituted or unsubstituted C1 to C10 alkylene, and R 6 to R 8 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, or substituted or unsubstituted C6 to C30 aryl.
  3. 3. The semiconductor photoresist composition of 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 of claim 3, wherein: X, Y and Z are identical to one another.
  5. 5. The semiconductor photoresist composition of claim 1, wherein: r 1 is selected from the group consisting of substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C20 heteroalkyl, substituted or unsubstituted C3 to C12 cycloalkyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C2 to C20 heteroaryl, substituted or unsubstituted C7 to C20 aralkyl, substituted or unsubstituted C4 to C20 heteroaralkyl, and substituted or unsubstituted C1 to C20 alkylcarbonyl.
  6. 6. The semiconductor photoresist composition of claim 1, wherein: R 1 is substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted 1-methylpropyl, substituted or unsubstituted 1, 1-dimethylpropyl, substituted or unsubstituted 2, 2-dimethylpropyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, or unsubstituted benzyl.
  7. 7. The semiconductor photoresist composition of claim 1, wherein: R 2 is hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, or substituted or unsubstituted C6 to C20 aryl, R 3 and R 4 are each independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, -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, a substituted or unsubstituted C3 to C10 cycloalkyl, a substituted or unsubstituted C6 to C20 aryl, -L 1 -C=C(R 6 )(R 7 ), or-L 2 -C≡C(R 8 ), R 5 is substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, -L 1 -C=C(R 6 )(R 7 ), or-L 2 -C≡C(R 8 ), L 1 and L 2 are substituted or unsubstituted C1 to C6 alkylene, and R 6 to R 8 are each independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, or substituted or unsubstituted C6 to C20 aryl.
  8. 8. The semiconductor photoresist composition of claim 1, wherein: r 2 is hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C10 alkenyl, or substituted or unsubstituted C2 to C10 alkynyl, R 3 and R 4 are each independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, -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, -L 1 -C=C(R 6 )(R 7 ), or-L 2 -C≡C(R 8 ), R 5 is substituted or unsubstituted C1 to C10 alkyl, -L 1 -C=C(R 6 )(R 7 ), or-L 2 -C≡C(R 8 ), L 1 and L 2 are substituted or unsubstituted C1 to C6 alkylene, and R 6 to R 8 are each independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C10 alkenyl, or substituted or unsubstituted C2 to C10 alkynyl.
  9. 9. The semiconductor photoresist composition of claim 1, wherein: The organometallic compound represented by chemical formula 1 is selected from the compounds listed in group 1: Group 1 。
  10. 10. The semiconductor photoresist composition of claim 1, wherein: The amount of the organometallic compound represented by chemical formula 1 is 0.5 to 30 wt% based on 100 wt% of the semiconductor photoresist composition.
  11. 11. The semiconductor photoresist composition of claim 1, further comprising other additives of surfactants, cross-linking agents, leveling agents, organic acids, quenchers, or combinations thereof.
  12. 12. A method of forming a pattern, comprising: forming an etching target layer on a substrate; coating the semiconductor photoresist composition according to any one of claims 1 to 11 on the etching target layer to form a photoresist film; exposing and developing the photoresist film to form a photoresist pattern on the photoresist film, and The etching target layer is etched using the photoresist pattern as an etching mask.
  13. 13. The method according to claim 12, wherein: The exposing and the developing of the photoresist film are performed using light having a wavelength in the range of 5 nm to 150 nm.
  14. 14. The method according to claim 12, wherein: the photoresist pattern has a width in the range of 5 nm to 100 nm.

Description

Semiconductor photoresist composition and method of forming pattern using the same Cross reference to related applications The present application claims priority and rights of korean patent application No. 10-2024-0156547 filed in the korean intellectual property office on month 11 and 6 of 2024, the entire disclosure of which is incorporated herein by reference. Technical Field One or more embodiments of the present disclosure relate to a semiconductor photoresist composition and a method of forming or providing a pattern using the same. Background Extreme ultraviolet (extreme ultraviolet, EUV) lithography is of interest as a key technology for the fabrication of next-generation semiconductor devices. EUV lithography is a patterning technique using EUV radiation (ray) having a wavelength of 13.5 nm as an exposure light source. According to EUV lithography, extremely fine patterns (e.g., 20 nm or less) may be formed or provided in an exposure process during the fabrication of semiconductor devices. Extreme Ultraviolet (EUV) lithography is achieved by development of compatible photoresists that may be practiced at spatial resolutions less than or equal to 16 nm. Efforts are underway to overcome the inadequate or inapplicable specifications of chemically amplified (CHEMICALLY AMPLIFIED, CA) photoresists, such as resolution, photospeed (photospeed), and feature roughness (or also referred to as line edge roughness (line edge roughness) or LER), commonly available for next generation devices. Intrinsic image blur (INTRINSIC IMAGE blurring) due to acid catalyzed reactions in the polymer type or class of photoresist can limit the resolution of small feature sizes, which has been a long term in electron beam (e-beam) lithography. Chemically Amplified (CA) photoresists are designed to achieve high sensitivity, but may be partially more difficult when performing EUV exposure because their elemental composition reduces the absorbance of the photoresist at 13.5 nm wavelengths and thus reduces its sensitivity. In addition, CA photoresists can have difficulties in small feature sizes due to roughness issues, and experiments have demonstrated that Line Edge Roughness (LER) of CA photoresists increases because photospeed is reduced in part due to the nature of the acid catalyst process. Thus, due to these drawbacks and problems with CA photoresists, a novel high performance photoresist is needed or desired in the semiconductor industry. In order to overcome the disadvantages of the Chemically Amplified (CA) organic photosensitive composition, an inorganic photosensitive composition has been studied. The inorganic photosensitive composition is used primarily or predominantly for negative patterning (negative tone patterning) that resists removal by developer compositions due to chemical modification by non-chemical amplification mechanisms. The inorganic composition contains an inorganic element whose EUV absorptivity is higher than that of hydrocarbon, and thus sensitivity can be ensured by a non-chemical amplification mechanism, and in addition, is less sensitive to random effects, and thus may have low line edge roughness and a small number of defects. Inorganic photoresists based on peroxypolyacids of tungsten mixed with tungsten, niobium, titanium and/or tantalum are radiation-sensitive materials (radiation-SENSITIVE MATERIAL) used for patterning. These materials are as effective as far ultraviolet (deep UV), X-ray and electron beam sources for or suitable for patterning large pitches of bilayer configurations or arrangements. Imaging of 15nm Half Pitch (HP) with a projected EUV exposure (projection EUV exposure) using a cationic hafnium metal oxide sulfate (HfSO x) material and a peroxy complexing agent shows the highest performance of non-CA photoresists and has practical photospeed approaching the requirements of EUV photoresists. However, hafnium metal oxide sulfate materials with peroxycomplexing agents have several practical drawbacks. First, these materials are coated as a corrosive sulfuric acid/hydrogen peroxide mixture and have inadequate or unsuitable shelf life stability. Second, it is challenging to alter the structure of the material in order to improve or enhance the properties as a composite mixture. Third, development should be performed in a very high concentration tetramethylammonium hydroxide (tetramethylammonium hydroxide, TMAH) solution of 25 wt.%, etc. Molecules comprising tin (Sn) have excellent or suitable absorption of extreme ultraviolet radiation. For organotin polymers therein, the alkyl ligands are dissociated by light absorption and/or secondary electrons generated therefrom, and are crosslinked with adjacent chains by oxo bonds, and thus enable negative patterning that may not be removed by an organic developer. Such organotin polymers exhibit greatly or significantly improved or enhanced sensitivity and maintain resolution and line edge roughness, but patterning characteristics should