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CN-122011265-A - Novel terpolymer photoresist resin and application thereof

CN122011265ACN 122011265 ACN122011265 ACN 122011265ACN-122011265-A

Abstract

The invention is suitable for the field of semiconductor manufacturing materials, and provides a novel terpolymer photoresist resin and application thereof, wherein the novel terpolymer photoresist resin is prepared from a novel acid-sensitive monomer (A1), a monomer Methyl Methacrylate (MMA) and a monomer 3-hydroxy-1-adamantyl-methacrylate (HAdMA). The application of the novel resin can obviously improve the photoetching patterns, in particular to improve the white edge problem, the photoresist pouring problem and the like in the photoetching patterns.

Inventors

  • LI PEIYUAN
  • Bai Qianhui
  • ZHU LIANGWEI
  • CHEN PENG
  • YIN HANG
  • MAO ZHIBIAO
  • XU CONGYING

Assignees

  • 宁波南大光电材料有限公司

Dates

Publication Date
20260512
Application Date
20260228

Claims (8)

  1. 1. The novel terpolymer photoresist resin is characterized by being prepared from a novel acid-sensitive monomer (A1), monomer Methyl Methacrylate (MMA) and monomer 3-hydroxy-1-adamantyl-methacrylate (HAdMA), wherein the chemical structure of the novel acid-sensitive monomer is (A1): (A1)。
  2. 2. The novel terpolymer photoresist resin according to claim 1, wherein the novel acid sensitive monomer reacts with monomer methyl methacrylate and monomer 3-hydroxy-1-adamantyl-methacrylate according to the following weight ratio to prepare the novel terpolymer photoresist resin: Novel acid-sensitive monomer, namely monomer methyl methacrylate, wherein monomer 3-hydroxy-1-adamantyl-methacrylate=20-40:30-50:20-40; most preferably, the novel acid sensitive monomer is the monomer methyl methacrylate, monomer 3-hydroxy-1-adamantyl-methacrylate=30:40:30.
  3. 3. A novel terpolymer photoresist resin according to claims 1-2, wherein the synthesis method of the novel terpolymer photoresist resin comprises the following steps: The novel acid-sensitive monomer, methyl methacrylate and 3-hydroxy-1-adamantyl-methacrylate are used as synthetic monomers, azodiisobutyronitrile (AIBN) is used as an initiator, 2-butanone is used as a solvent, a one-pot method is adopted, heating reflux is carried out for 10 hours, cooling is carried out to room temperature after reaction is finished, a product solution is obtained, and after solvent n-heptane is added for precipitation, filtration and drying are carried out, thus obtaining the novel terpolymer photoresist resin.
  4. 4. A method of synthesizing a novel terpolymer photoresist resin according to claim 3 wherein the initiator Azobisisobutyronitrile (AIBN) is 1% to 20%, preferably 1% to 10%, most preferably 5% by weight of all monomers.
  5. 5. A method of synthesizing a novel terpolymer photoresist resin according to claims 3-4 wherein said solvent 2-butanone is used to prepare the monomer solution at a concentration of 10% wt to 50% wt, preferably 30% wt to 40% wt, most preferably 35% wt.
  6. 6. A method of synthesizing a novel terpolymer photoresist resin according to claims 3-5 wherein the weight of solvent n-heptane is from 6 to 20 times, preferably from 8 to 15 times, most preferably 10 times the weight of the product solution.
  7. 7. The method for synthesizing a novel terpolymer photoresist resin according to claim 3-6, wherein the temperature and time of the drying are 80 ℃ and 6 hours.
  8. 8. A photoresist, wherein the photoresist is prepared from the novel terpolymer resin of claims 1-7.

Description

Novel terpolymer photoresist resin and application thereof Technical Field The invention belongs to the field of semiconductor manufacturing materials, and particularly relates to novel terpolymer photoresist resin and application thereof. Background The photoresist is mainly used in the micro-nano pattern processing process, and is also commonly used in the fields of liquid crystal display, printed circuits and the like besides being used for manufacturing chips of various technical nodes in integrated circuits and very large scale integrated circuits. In the development history of integrated circuits, moore predicts that the number of transistors on an integrated circuit doubles every 18-24 months, but since the "process" of the transistors reaches 7 nm, the number growth rate has begun to deviate gradually from the linear growth relationship of Moore's law, and how to develop a photolithography machine with shorter exposure wavelength and finer photolithography and a photoresist with better photolithography performance to match the development rhythm of Moore's law on the performance requirement of the integrated circuit still faces a plurality of challenges. In the 193nm-ArF photoresist resin field, a chemical amplification concept is proposed by Ito, willison, frechet in 1982, and the core of the chemical amplification photoresist is that the chemical amplification photoresist resin contains acid-sensitive groups and photoacid generators, the photoacid generators can be decomposed in the exposure process, free radicals, cations and other products generated by the decomposition can act with proton donors of resin, solvent and the like in a glue film to generate super strong protonic acid, and the generated photoacid is diffused to acid-sensitive chemical groups of the resin in an exposure area along with the rising of temperature in a relatively strong molecular thermal motion in the post baking process to act with the protective groups of the acid-sensitive groups, so that the protective groups are removed, the glue film at the exposure part can be dissolved in a developing solution, the acid-sensitive groups can generate new photoacid while being broken, the unbroken acid-sensitive groups can be circularly generated in theory, the acid-sensitive groups continuously attack the photoacid, the acid plays a role of acid catalysis, and the sensitivity of the photoresist is greatly improved. Although the theoretical method of chemical amplification was proposed as early as 1982, no application precedent is given, and attention and importance are not paid until IBM has invented a photoresist containing p-t-butoxycarbonyl oxystyryl in the 80 th 20 th century, and has realized application under the condition that anisole is a developing solution, the sensitivity of exposure is 100-200 times higher than that of the non-chemically amplified photoresist, and so far, the application of the chemical amplification technology has not begun to "break ice" in the field of integrated circuits. The chemical amplification method overcomes the key problem of the rapid reduction of exposure efficiency caused by the reduction of exposure power along with the wavelength of an exposure light source in large-scale industrial application, and the design of the ArF photoresist still maintains and maintains the key design thought. Poly (methyl) acrylate has the advantages of high transmission to ArF excimer laser, simple synthesis process, good adhesion performance and mechanical performance, and the like, but poly (methyl) acrylate which is firstly applied to ArF photoresist is a terpolymer obtained by polymerizing methyl methacrylate, methacrylic acid and n-butyl methacrylate, and is developed by IBM/MIT Lincoln laboratory in 1993 and is prepared into simple ArF photoresist with one acid generator component and is applied to a photoetching process with resolution of 0.22 mu m, but subsequent research discovers that the main chain of the resin of the type is a linear structure, and the ester bond connecting the main chain and the side chain increases the oxygen element content in the resin, so that a glue film prepared from the photoresist of the type shows poor etching resistance in a plasma etching process. In order to improve the etching resistance of the resin synthesized by the system in the plasma etching processing process, further researches show that the introduction of the structure with high carbon-hydrogen ratio such as adamantyl, norbornyl, cubic alkyl and the like on the side chain of the resin can effectively increase the carbon content in the resin to improve the etching resistance, and the typical polymethacrylate for ArF photoetching after the structure with high carbon-hydrogen ratio is introduced. In addition, the structure of the side chain connecting group is changed and regulated, so that the hydrophilic and hydrophobic properties, the adhesion property to a substrate material, the optical transmission prop