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CN-116125747-B - Extreme ultraviolet non-chemical amplification photoresist and preparation method and application thereof

CN116125747BCN 116125747 BCN116125747 BCN 116125747BCN-116125747-B

Abstract

The invention relates to an extreme ultraviolet non-chemical amplification photoresist, a preparation method and application thereof, the extreme ultraviolet non-chemical amplification photoresist has excellent indexes and processing performance, and meets the application of the EUV lithography field. The extreme ultraviolet non-chemical amplification photoresist has the characteristics of simple preparation, easily available raw materials, small operation difficulty and wide applicability.

Inventors

  • WANG YAXIONG
  • ZHU HAILING
  • Peng Shenlai
  • ZHAO YUNCHUAN

Assignees

  • 中瀚新材料科技有限公司

Dates

Publication Date
20260508
Application Date
20221220

Claims (20)

  1. 1. The extreme ultraviolet non-chemically amplified photoresist is characterized in that the extreme ultraviolet non-chemically amplified photoresist is a polycarbonate resin, and the polycarbonate resin has a structure shown in a formula I: A formula I; wherein m and n are independently integers of 1 to 200; r 1 is a structural unit formed by a first monomer, wherein the first monomer is dihydric alcohol; R 2 is a structural unit formed by a second monomer, and the second monomer has the following structure: ; wherein x is an integer of 2 to 12; the first monomer is selected from any one or a combination of at least two of the following structures: 。
  2. 2. the euv non-chemically amplified resist of claim 1, wherein the second monomer is prepared from a starting material comprising 4-hydroxystyrene and dithiol.
  3. 3. The euv non-chemically amplified resist of claim 2, wherein said dithiol comprises any of ethanedithiol, 1, 2-propanedithiol, 1, 3-propanedithiol, 1, 4-butanedithiol, 2, 3-butanedithiol, 1, 5-pentanedithiol, 1, 6-hexanedithiol, 1, 8-octanedithiol, 1, 9-nonanedithiol, 1, 10-decanedithiol, or n-dodecanethiol.
  4. 4. The euv non-chemically amplified photoresist of claim 1, wherein said polycarbonate-based resin comprises any one or a combination of at least two of the following compounds: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 ; Wherein each m is independently an integer of 1 to 200; n is each independently an integer of 1 to 200.
  5. 5. The euv non-chemically amplified resist of claim 1, wherein said polycarbonate-based resin has an intrinsic viscosity of 0.52 to 1.01 dL/g.
  6. 6. The euv non-chemically amplified resist according to claim 1, wherein the number average molecular weight of the polycarbonate-based resin is 9657 to 25896 g/mol.
  7. 7. The euv non-chemically amplified resist of claim 1, wherein said polycarbonate-based resin has a molecular weight distribution index of 1.6 to 2.4.
  8. 8. The euv non-chemically amplified resist of claim 1, wherein said polycarbonate-based resin has a glass transition temperature of 127 to 151 ℃.
  9. 9. The euv non-chemically amplified resist of claim 1, wherein the thermal decomposition temperature of the polycarbonate resin is at least 229 ℃.
  10. 10. A method of preparing the extreme ultraviolet non-chemically amplified photoresist according to any of claims 1 to 9, comprising the steps of: And mixing diphenyl carbonate, a first monomer forming an R 1 structural unit and a second monomer forming an R 2 structural unit, and performing bulk melt polymerization to obtain the polycarbonate resin, namely the extreme ultraviolet non-chemically amplified photoresist.
  11. 11. The method of preparing according to claim 10, wherein the method of preparing the second monomer comprises the steps of: (a) Mixing 4-hydroxystyrene, dithiol, an initiator and a solvent, and performing a crosslinking reaction to obtain a bisphenol monomer with a thioether structure; (b) Mixing a thioether-structure bisphenol monomer, m-chloroperoxybenzoic acid and a solvent, and reacting to obtain a sulfone-structure bisphenol monomer which is the second monomer.
  12. 12. The method of claim 11, wherein in step (a), the initiator comprises a photoinitiator.
  13. 13. The method of claim 11, wherein the initiator comprises any one or a combination of at least two of benzoin dimethyl ether, benzoin diethyl ether, benzoin isopropyl ether, or benzoin butyl ether.
  14. 14. The method of claim 11, wherein the solvent in step (a) and step (b) comprises any one or a combination of at least two of tetrahydrofuran, butanone, or cyclopentanone.
  15. 15. The method of claim 11, further comprising separating and drying after the crosslinking reaction.
  16. 16. The process of claim 11, wherein in step (b), the temperature of the reaction is from 10 ℃ to 40 ℃.
  17. 17. The method of claim 11, wherein in step (b), the post-reaction further comprises washing and drying.
  18. 18. The method according to claim 10, wherein the ratio of the number of moles of diphenyl carbonate to the total number of moles of the first monomer and the second monomer is 1.05 to 1.1.
  19. 19. The method of claim 10, wherein the bulk melt polymerized feedstock further comprises a catalyst.
  20. 20. The method of claim 10, wherein the bulk melt polymerized feedstock further comprises an auxiliary agent.

Description

Extreme ultraviolet non-chemical amplification photoresist and preparation method and application thereof Technical Field The invention relates to the technical field of photoresist, in particular to an extreme ultraviolet non-chemical amplification photoresist, and a preparation method and application thereof. Background Photoresists, also known as photoresists, can undergo a change in solubility upon irradiation with a light source such as ultraviolet light, electron beam, or the like, and become soluble or insoluble in a developer. Photoresists are largely classified into two main types, namely, a substance that is insoluble in a developer under irradiation of a light source becomes soluble in the developer, called a positive resist, and a substance that is insoluble in the developer under irradiation becomes a negative resist, depending on the change of the property after irradiation. Photoresist is one of the key materials in the photolithography process, and the quality of the photoresist directly affects the process accuracy of semiconductor integrated circuits and devices. With the development of semiconductor manufacturing, photolithography is distinguished from exposure wavelength, and is successively subjected to G-line (436 nm), I-line (365 nm), krF (248 nm), arF (193 nm, including dry and immersion) and extreme ultraviolet (EUV, 13.5 nm) lithography. Techniques using EUV lithography have been considered as the primary option for mass production of 10-16 nm node chips, but this requires higher photoresist sensitivity and resolution to ensure accurate transfer of the pattern on the reticle to the silicon wafer. Currently, polymeric materials for EUV photoresists are classified into chemically amplified photoresists (CARs) which require the use of photoacid generators (PAGs) to generate large amounts of strong acid hydrogen ions, but photoacid diffusion causes large linewidth roughness, and non-chemically amplified photoresists (non-CARs) which do not completely eliminate, although bonding PAG molecules to polymer molecular chains can greatly reduce acid diffusion. CN107991842a discloses the use of a polycarbonate formed by alternating copolymerization of carbon dioxide and at least one alkylene oxide as an electron beam resist material. The polycarbonate disclosed by the method has the characteristics of high sensitivity, higher resolution and higher contrast. However, the polycarbonate synthesis method needs to use an autoclave, needs to react for 48 hours under the atmosphere of 3MPa carbon dioxide, and needs to use the carbon dichloride for dissolution and then use methanol for precipitation, filtration and purification. The reaction conditions and steps are complex. CN111253563a discloses an application of polycarbonate as ultraviolet photoresist material, and the disclosed polycarbonate introduces photosensitive groups or/and acid generating groups into side chains to reduce diffusion of photoacid to unexposed areas, and enables the photoresist to have polarity inversion and main chain fracture after exposure, so that the polycarbonate has the characteristics of low line edge roughness, high sensitivity, high resolution and high contrast. However, such polycarbonate photoresist materials, which are essentially chemically amplified photoresists (CARs), require the use of photoacid generators (PAGs) to generate large amounts of strong acid hydrogen ions, which, although introducing photoacid groups onto the polymer side chains, as previously described, are always subject to photoacid diffusion, which is not as good as non-chemically amplified photoresists in terms of sensitivity and line width roughness. In summary, development of a novel polycarbonate resin as a non-chemically amplified photoresist material and application thereof in the field of Extreme Ultraviolet (EUV) lithography is of great importance. Disclosure of Invention Aiming at the defects of the prior art, the invention aims to provide an extreme ultraviolet non-chemical amplification photoresist, a preparation method and application thereof, wherein the extreme ultraviolet non-chemical amplification photoresist has excellent indexes and processability, and meets the application in the field of EUV lithography. The extreme ultraviolet non-chemical amplification photoresist has the characteristics of simple preparation, easily available raw materials, small operation difficulty and wide applicability. To achieve the purpose, the invention adopts the following technical scheme: In a first aspect, the present invention provides an extreme ultraviolet non-chemically amplified photoresist comprising a polycarbonate resin having a structure according to formula I: Wherein m and n are each independently integers between 1 to 200 (e.g., 5, 10, 20, 40, 60, 80, 100, 120, 140, 160, 180, etc.); r 1 is a structural unit formed by a first monomer, wherein the first monomer is dihydric alcohol; R 2 is a structural unit formed by a second monom