Characterization of high-resolution HafSOx inorganic resists

Inorganic resists are of considerable interest for advanced lithography at the nanoscale due to the potential for high resolution, low line width roughness (LWR), and high sensitivity. Historically inorganic resists suffered from low sensitivity, however approaches have been identified to increase sensitivity while maintaining high contrast. An aqueous precursor of Hf(OH)4-2x-2y(O2)x(SO4)y·qH2O (HafSOx) has been demonstrated with excellent sensitivity to EUV and electrons, while still obtaining high resolution and low LWR. In this work, we characterize both HafSOx precursor solutions and spin-coated thin films using high-resolution transmission electron microscopy (HR-TEM) with energy-dispersive X-ray spectroscopy (EDS) elemental analysis. HR-TEM of precursor solutions drop cast onto TEM grids confirmed the presence of nanoscale particles. HR-TEM cross sectional images showed that spin-coated HafSOx films are initially uniform in appearance and composition for thin (12 nm) films, however thicker (30 nm) films display segregation of species leading to multilayer structures. Regardless of film thickness, extended exposure to the high energy TEM electron beam induces significant migration of oxygen species to the Si interface. These species result in the formation of SiOx layers that increase in thickness with an increase in TEM electron beam dose. Sulfate is also very mobile in the films and likely assists in the significant condensation exhibited in completely processed films.

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