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<p>The miniaturization of semiconductor devices is constrained by the resolution-sensitivity-roughness (RLS) trade-off in photoresists. Tin-oxo clusters (TOCs) provide a chemically tunable platform where performance can be effectively modulated through ligand design. Although alkenyl groups promote cross-linking and fluorinated moieties enhance both solubility and etch resistance, their cooperative function within one molecular framework remains unclear. Here, we design a series of <b>Sn</b><sub><b>2</b></sub>-oxo clusters with ligands containing both alkenyl and trifluoromethyl (–CF<sub>3</sub>) groups (<b>Sn</b><sub><b>2</b></sub><b>-1</b>), only alkenyl (<b>Sn</b><sub><b>2</b></sub><b>-2</b>), and only–CF<sub>3</sub> (<b>Sn</b><sub><b>2</b></sub><b>-3</b>). In electron beam lithography (EBL), <b>Sn</b><sub><b>2</b></sub><b>-1</b> achieves higher resolution (13.56 nm) and lower line-edge roughness (LER) than <b>Sn</b><sub><b>2</b></sub><b>-2</b>, despite a moderate sensitivity cost. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) reveal a dual intramolecular mechanism: the–CF<sub>3</sub> group withdraws electron density from the alkenyl moiety, suppressing uncontrolled cross-linking, while the cleaved fluorine radicals are locally scavenged by the adjacent carbon-centered radicals. This work establishes a ligand-design strategy based on alkenyl-fluorine synergy effects, providing critical insights for advancing high-performance TOC-based photoresists.</p>

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Alkenyl-fluorine synergy for enhanced resolution and reduced line-edge roughness in tin-oxo cluster photoresists

  • 期刊论文

  • 发表日期：

    2026年7月16日

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  • Siming Qi,
  • Zuohu Zhou,
  • Fangfang Liu,
  • Jian Wei,
  • Aibing Yang,
  • Lanjun Guo,
  • Jun Zhao,
  • Wolfgang Schmitt,
  • Zhuo Jiang,
  • Ni Zhen,
  • Lei Zhang

摘要

The miniaturization of semiconductor devices is constrained by the resolution-sensitivity-roughness (RLS) trade-off in photoresists. Tin-oxo clusters (TOCs) provide a chemically tunable platform where performance can be effectively modulated through ligand design. Although alkenyl groups promote cross-linking and fluorinated moieties enhance both solubility and etch resistance, their cooperative function within one molecular framework remains unclear. Here, we design a series of Sn2-oxo clusters with ligands containing both alkenyl and trifluoromethyl (–CF3) groups (Sn2-1), only alkenyl (Sn2-2), and only–CF3 (Sn2-3). In electron beam lithography (EBL), Sn2-1 achieves higher resolution (13.56 nm) and lower line-edge roughness (LER) than Sn2-2, despite a moderate sensitivity cost. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) reveal a dual intramolecular mechanism: the–CF3 group withdraws electron density from the alkenyl moiety, suppressing uncontrolled cross-linking, while the cleaved fluorine radicals are locally scavenged by the adjacent carbon-centered radicals. This work establishes a ligand-design strategy based on alkenyl-fluorine synergy effects, providing critical insights for advancing high-performance TOC-based photoresists.