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CN-121995697-A - Semiconductor photoresist composition and method of forming pattern using the same

CN121995697ACN 121995697 ACN121995697 ACN 121995697ACN-121995697-A

Abstract

A semiconductor photoresist composition and a method of forming a pattern using the same are provided. The semiconductor photoresist composition includes an organometallic compound, a polymer including a first structural unit represented by chemical formula M-1 and a second structural unit represented by chemical formula 2 or chemical formula 3, and a solvent. The descriptions of chemical formula M-1, chemical formula 2 and chemical formula 3 are as described in the specification. The present application can realize a pattern having improved sensitivity and line edge roughness characteristics.

Inventors

  • Wen Chengri
  • Jin Linggen
  • REN XIANGJUN
  • Han Meilian

Assignees

  • 三星SDI株式会社

Dates

Publication Date
20260508
Application Date
20251106
Priority Date
20241106

Claims (20)

  1. 1. A semiconductor photoresist composition comprising: an organometallic compound; a polymer, comprising: A first structural unit, and A second structural unit comprising a second structural unit, The first structural unit is represented by the formula M-1, and The second structural unit is represented by chemical formula 2 or chemical formula 3, and The solvent is used for the preparation of the aqueous solution, [ Chemical formula M-1] [ Chemical formula 2] [ chemical formula 3] , Wherein in chemical formula M-1, chemical formula 2 and chemical formula 3, R 1 to R 3 are each independently hydrogen or substituted or unsubstituted C1 to C10 alkyl, L 1 and L 2 are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof, X 1 is a single bond, -O-, -S (=O) 2 -、-C(=O)-、-C(=O)O-、-OC(=O)、-OC(=O)O-、-NR a -, or a combination thereof, R a is hydrogen, deuterium, or a substituted or unsubstituted C1 to C10 alkyl, X 2 is a single bond, -C (=o) -, or a substituted or unsubstituted C1 to C10 alkylene, X 3 is a single bond, -L 4 , -O-, or a substituted or unsubstituted C1 to C10 alkylene, L 4 is a substituted or unsubstituted C1 to C10 alkylene, R 4 is hydrogen, fluoro, hydroxy, substituted or unsubstituted C1 to C20 alkyl, or a combination thereof, At least one selected from R 4 、L 1 and L 2 includes fluorine and hydroxyl, R 5 is hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof, R 6 to R 8 are each independently hydrogen, halogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof, M1 and m2 are each independently an integer of 1 to 4, and Is the connection point.
  2. 2. The semiconductor photoresist composition of claim 1, wherein The first structural unit is represented by chemical formula 1: [ chemical formula 1] And (2) and Wherein in the chemical formula 1, R 1 is hydrogen, or substituted or unsubstituted C1 to C10 alkyl, R c 、R d 、R e 、R f and R 4 are each independently hydrogen, fluorine, hydroxyl, substituted or unsubstituted C1 to C20 alkyl, or a combination thereof, M3 and m4 are each independently an integer of 1 to 10, X 1 is a single bond, -O-, -S (=O) 2 -、-C(=O)-、-C(=O)O-、-OC(=O)、-OC(=O)O-、-NR a -, or a combination thereof, R a is hydrogen, deuterium, or a substituted or unsubstituted C1 to C10 alkyl, and At least one selected from R c 、R d 、R e 、R f and R 4 includes fluorine and hydroxyl.
  3. 3. The semiconductor photoresist composition of claim 1, wherein The first structural unit is at least one selected from group I: Group I And (2) and Wherein in the group I of the two groups, R 1 is each independently hydrogen or methyl, and Is the connection point.
  4. 4. The semiconductor photoresist composition of claim 1, wherein The second structural unit is represented by chemical formula 2-1 or chemical formula 2-2: [ chemical formula 2-1] [ chemical formula 2-2] And (2) and Wherein in chemical formula 2-1 and chemical formula 2-2, R 2 、R 5 、R 6 and m 1 are as defined in formula 2, and Is the connection point.
  5. 5. The semiconductor photoresist composition of claim 4, wherein The second structural unit is represented by any one selected from chemical formulas 2-1- (i) to 2-1- (iv): [ chemical formula 2-1- (i) ] [ chemical formula 2-1- (ii) ] [ Chemical formula 2-1- (iii) ] [ chemical formula 2-1- (iv) ] And (2) and Wherein in the formulae 2-1- (i) to 2-1- (iv), R 2 is hydrogen or methyl, and the hydrogen is methyl, R 5 、R 5a and R 5b are each independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof, R 6a 、R 6b 、R 6c and R 6d are each independently hydrogen, halogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof, and Is the connection point.
  6. 6. The semiconductor photoresist composition of claim 4, wherein The second structural unit is represented by any one selected from chemical formulas 2-2- (i) to 2-2- (iii): [ chemical formula 2-2- (i) ] [ chemical formula 2-2- (ii) ] [ chemical formula 2-2- (iii) ] And (2) and Wherein in the formulae 2-2- (i) to 2-2- (iii), R 2 is hydrogen or methyl, and the hydrogen is methyl, R 5 is hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof, R 6a 、R 6b 、R 6c and R 6d are each independently hydrogen, halogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof, and Is the connection point.
  7. 7. The semiconductor photoresist composition of claim 1, wherein The second structural unit is represented by chemical formula 3-1 or chemical formula 3-2: [ chemical formula 3-1] [ chemical formula 3-2] And (2) and Wherein in chemical formula 3-1 and chemical formula 3-2, R 3 、R 8 、R 7 、L 4 and m2 are as defined in chemical formula 3, R 17 and R 18 are each independently hydrogen, halogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof, M5 is one of integers from 0 to 10, and Is the connection point.
  8. 8. The semiconductor photoresist composition of claim 7, wherein The second structural unit is represented by any one selected from chemical formulas 3-1- (i) to 3-1- (iii): [ chemical formula 3-1- (i) ] [ chemical formula 3-1- (ii) ] [ Chemical formula 3-1- (iii) ] And (2) and Wherein in the formulae 3-1- (i) to 3-1- (iii), R 3 is hydrogen or methyl, and the hydrogen is methyl, R 7 is hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof, R 17 and R 18 are each independently hydrogen, halogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof, R 8a 、R 8b 、R 8c and R 8d are each independently hydrogen, halogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof, M5 is one of integers from 0 to 10, and Is the connection point.
  9. 9. The semiconductor photoresist composition of claim 7, wherein The second structural unit is represented by any one selected from chemical formulas 3-2- (i) to 3-2- (iii): [ chemical formula 3-2- (i) ] [ chemical formula 3-2- (ii) ] [ Chemical formula 3-2- (iii) ] And (2) and Wherein in the formulae 3-2- (i) to 3-2- (iii), R 3 is hydrogen or methyl, and the hydrogen is methyl, R 7 is hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof, L 4 is a substituted or unsubstituted C1 to C10 alkylene, R 8a 、R 8b 、R 8c and R 8d are each independently hydrogen, halogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof, and Is the connection point.
  10. 10. The semiconductor photoresist composition of claim 1, wherein The second structural unit is at least one selected from the group consisting of groups II: group II And (2) and Wherein in the group II of the two groups, R 2 and R 3 are each independently hydrogen or methyl, and Is the connection point.
  11. 11. The semiconductor photoresist composition of claim 1, wherein The polymer includes 30 to 90 mole% of the first structural unit and 10 to 70 mole% of the second structural unit.
  12. 12. The semiconductor photoresist composition of claim 1, wherein The polymer has a weight average molecular weight of 1,000 g/mol to 50,000 g/mol.
  13. 13. The semiconductor photoresist composition of claim 1, wherein The polymer is present in an amount of 0.1 to 10 weight percent based on 100 weight percent of the total weight of the semiconductor photoresist composition.
  14. 14. The semiconductor photoresist composition of claim 1, wherein The organometallic compound is present in an amount of 0.5 to 30 weight percent based on 100 weight percent of the total weight of the semiconductor photoresist composition.
  15. 15. The semiconductor photoresist composition of claim 1, wherein The organometallic compound includes at least one selected from the group consisting of an organoxy group and an organocarbonyloxy group.
  16. 16. The semiconductor photoresist composition of claim 1, wherein The organometallic compound is represented by chemical formula 4: [ chemical formula 4] And (2) and Wherein in the chemical formula 4, R 10 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 C6 to C30 aralkyl, R 11 to R 13 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 C6 to C30 aralkyl, alkoxy OR aryloxy-OR g , carboxyl -OC(=O)R h 、-NR i R j 、-NR k (COR l )、-NR m C(NR n )R o 、-SR p 、 OR-SC (=O) R q , Wherein R g 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, or a combination thereof, Wherein R h 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, Wherein 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, Wherein R k and R l 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, Wherein R m 、R n and R o 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, Wherein R p 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 Wherein R q 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, At least one of R 11 to R 13 is selected from -OR g 、-OC(=O)R h 、-NR i R j 、-NR k (COR l )、-NR m C(NR n )R o 、-SR p 、 or-SC (=o) R q .
  17. 17. The semiconductor photoresist composition of claim 16, wherein At least one of R 11 to R 13 is selected from-OR g OR-OC (=o) R h .
  18. 18. The semiconductor photoresist composition of claim 17, wherein R 10 is a substituted or unsubstituted C1 to C8 alkyl, a substituted or unsubstituted C3 to C8 cycloalkyl, a substituted or unsubstituted C2 to C8 aliphatically unsaturated organic group comprising one or more double or triple bonds, a substituted or unsubstituted C6 to C20 aryl, a substituted or unsubstituted C4 to C20 heteroaryl, carbonyl, ethoxy, propoxy, or a combination thereof, R g is substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof, and R h 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.
  19. 19. The semiconductor photoresist composition of claim 1, wherein The organometallic compound is represented by chemical formula 5 or chemical formula 6: [ chemical formula 5] R 14 z SnO (2-(z/2)-(x/2)) (OH) x , Wherein in the chemical formula 5, R 14 is a C1 to C31 hydrocarbon radical, 0 < Z≤2, and 0 <(z+x)≤4; [ Chemical formula 6] R 15 a1 Sn b1 X c1 Y d1 , an Wherein in the chemical formula 6, R 15 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, selenium or tellurium, and the like, Y is-OR r OR-OC (=O) R s , Wherein R r 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 s 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 A1, b1, c1 and d1 are each independently integers of 1 to 20.
  20. 20. A method of forming a pattern, comprising: forming an etching target layer on a substrate; coating the semiconductor photoresist composition of any one of claims 1 to 19 on the etching target layer to form a photoresist film; Patterning the photoresist film to form a photoresist pattern, and And etching the etching target layer by using the photoresist pattern as an etching mask.

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. 10-2024-0156548 filed in the korean intellectual property office on month 11 and 6 of 2024, the entire contents of which are incorporated herein by reference. Technical Field The present disclosure relates to a semiconductor photoresist composition and a method of forming a pattern using the same. Background Extreme ultraviolet (extreme ultraviolet, EUV) lithography has been attracting attention as an essential technique for manufacturing next-generation semiconductor devices, such as semiconductor chips. The EUV lithography is a patterning technique using EUV rays having a wavelength of 13.5 nm as an exposure light source. It is known that extremely fine patterns (e.g., less than or equal to 20 nanometers) can be formed during an exposure process for manufacturing semiconductor devices, such as semiconductor chips. The implementation of EUV lithography relies on the development of compatible photoresists that enable spatial resolution of less than or equal to 16 nanometers. Currently, efforts are underway to address the issues of undersides such as resolution, photospeed (photospeed), and feature roughness (also known as line edge roughness (line edge roughness) or LER) of chemically amplified (CHEMICALLY AMPLIFIED, CA) photoresists for next generation devices. Intrinsic image blur (INTRINSIC IMAGE blurring) due to acid catalyzed reactions in these polymer type(s) photoresists can limit resolution at small feature sizes, which is a long standing challenge in electron beam (e-beam) lithography. Chemically Amplified (CA) photoresists are designed to achieve high sensitivity, but their typical elemental composition reduces the absorbance of the photoresist at 13.5 nm wavelength, thus reducing its sensitivity. Thus, a Chemical Amplification (CA) photoresist may face more difficulties in performing EUV exposure. Furthermore, CA photoresists can present difficulties at small feature sizes due to roughness issues. Experimentally, the Line Edge Roughness (LER) of CA photoresists increases with decreasing photospeed due in part to the nature of the acid catalyst process. Accordingly, a novel high performance photoresist is desired or needed in the semiconductor industry to address these drawbacks and problems with CA photoresists. To overcome the above-described drawbacks of Chemically Amplified (CA) organic photosensitive compositions, inorganic photosensitive compositions have been studied. Inorganic photosensitive compositions are primarily or predominantly used for negative patterning (negative tone patterning) and exhibit resistance to removal by developer compositions due to chemical modification by non-chemical amplification mechanisms. The inorganic composition contains an inorganic element having an EUV absorptivity higher than that of hydrocarbon, and thus ensures sensitivity by a non-chemical amplification mechanism. Furthermore, the inorganic composition is less sensitive to random effects and is known to have low line edge roughness and fewer defects. Inorganic photoresists based on peroxy polyacids of tungsten mixed with tungsten, niobium, titanium and/or tantalum have been reported as radiation-sensitive materials for patterning. These materials are effective in patterning large pitches of bilayer configurations as far ultraviolet (deep UV), X-ray, and electron beam sources. Improved performance is observed when a cationic metal oxide hafnium sulfate (HfSO x) material is used with a peroxycomplexing agent to image a 15 nanometer Half Pitch (HP) by projection EUV exposure. This system exhibits high performance for non-CA photoresists and has practical photospeed approaching EUV photoresist requirements. However, metal oxide hafnium sulfate materials with peroxycomplexing agents have some practical drawbacks. First, these materials are coated with a corrosive sulfuric acid/hydrogen peroxide mixture and have insufficient stability over shelf life. Second, as a composite mixture, it is challenging to change the structure to achieve performance improvements. Third, development should be performed in a solution of tetramethylammonium hydroxide (tetramethylammonium hydroxide, TMAH) at extremely high concentrations, e.g., 25 wt.% or higher, such as 25 wt.%. In order to solve these problems, research has been focused on developing molecules containing tin, which have excellent or suitable absorptivity to extreme ultraviolet rays. For organotin polymers among these tin-containing molecules (e.g., tin-containing molecules), the alkyl ligands are dissociated by light absorption or secondary electrons generated therefrom. The dissociated alkyl ligands then crosslink with adjacent chains through oxo bonds, enabling negative patterning that is not removable by the organic developer. While such organotin polymers