Novel Etch-Resistant Molecular Glass Photoresist Based on Pyrene Derivatives for Electron Beam Lithography

Novel t-butyloxycarbonyl-protected molecular glass photoresists with pyrene as the core (Pyr-8Boc and Pyr-4Boc) were designed and synthesized. The thermal stability and film-forming ability were measured to assess their applicability for lithography. Pyr-Boc (Pyr-8Boc and Pyr-4Boc) photoresists were evaluated by high-resolution electron beam lithography (EBL), acting as chemically amplified resists. Pyr-4Boc showed a better lithography performance, achieving 25 nm line/space patterns at the dose of 50 μC/cm2. Under SF6/O2 plasma, the etch selectivity of the Pyr-4Boc photoresist to silicon was 12.3, which is twice that of the commercially available poly­(methyl methacrylate) photoresist (950 k). The lithography mechanism of EBL was further investigated. Theoretical calculations of HOMO/LUMO orbital energies, cyclic voltammetry, and fluorescence quenching experiments were conducted to confirm the electron-transfer reactions between the Pyr-Boc and photoacid generator. The study provides an option of high sensitivity and etch-resistant photoresist for EBL.