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The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
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Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
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The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
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Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is...
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Versatile Reactive Gradient Block Copolymer System for Highly Robust Nanopatterns With Spontaneous Vertical

Jeehyun Hong1, Yemin Park1, Gyu Rac Lee1,2

  • 1Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology, 291 Daehak-ro, Yuseong-gu, Daejeon, 34141, Republic of Korea.

Small (Weinheim an Der Bergstrasse, Germany)
|December 13, 2025
PubMed
Summary
This summary is machine-generated.

This study introduces a novel reactive polymer gradient-random block copolymer (GRC-BCP) for creating precisely controlled, vertically oriented nanostructures. This breakthrough enables enhanced semiconductor device performance and diverse material applications.

Keywords:
EUV lithographydirected self‐assemblygradient‐random copolymershigh‐χ block copolymerspost‐polymerization modification

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Area of Science:

  • Materials Science
  • Polymer Chemistry
  • Nanotechnology

Background:

  • Directed self-assembly of high-χ block copolymers (BCPs) is crucial for semiconductor device performance.
  • Conventional BCPs face limitations in chemical tunability and vertical orientation, hindering practical applications.

Purpose of the Study:

  • To develop a novel reactive polymer gradient-random block copolymer (GRC-BCP) system.
  • To enable the fabrication of vertically oriented nanostructures with tunable properties on diverse substrates.

Main Methods:

  • Synthesis of poly(methyl methacrylate-block-(pentafluorophenyl acrylate-gradient-styrene)) GRC-BCP.
  • Utilizing the tailored gradient block structure for vertical pattern formation without surface neutralization.
  • Application as a photoresist height enhancer in extreme ultraviolet lithography.

Main Results:

  • Achieved vertically oriented patterns with controlled linewidths from 7 to 13 nm in organosilicon and organotin GRC-BCPs.
  • Demonstrated the GRC-BCP's utility as a robust photoresist height enhancer.
  • Fabricated Si patterns with high aspect ratio (5.78) at 13 nm half-pitch, exhibiting low line edge and width roughness.

Conclusions:

  • The developed reactive polymer GRC-BCP system offers efficient synthesis and broad utility.
  • This platform material is suitable for applications requiring vertically oriented patterns with specific functionalities.
  • The GRC-BCP system is expected to advance semiconductor fabrication and other nanotechnology fields.