Medusa 82—Hydrogen silsesquioxane based high sensitivity negative-tone resist with long shelf-life and grayscale lithography capability

Abstract

The high suitability of hydrogen silsesquioxane (HSQ) as e-beam resist has long been known. Despite its undoubtedly good and reliable properties, HSQ nevertheless proves to be problematic in certain aspects due to its relatively short shelf-life and the small processing window between coating preparation and exposure. We thus intended to optimize the silsesquioxane with respect to a prolonged shelf-life and larger processing window while retaining all advantages like the high silicon content for high etch resistance and high pattern resolution. Our combined knowledge resulted in the development of the hydrogen silsesquioxane-based e-beam resist Medusa 82 with improved characteristics. Medusa 82 can be processed with HSQ standard procedures but allows for a delay of several weeks between layer preparation and exposure under standard conditions. Medusa 82 resist compositions tolerate storage periods of several weeks at room temperature. In addition, we generated and investigated variants of Medusa 82, which offer the possibility for exposure with less energy to cross-link the resist. Furthermore, weaker alkaline developers can be applied. A postexposure bake of these new Medusa 82 variants provides a significant enhancement of sensitivity and contrast. In this context, applications of Medusa 82 in deep to extreme ultraviolet and grayscale lithography are described. The use of glasslike resists with moderate electron beam sensitivity has the potential to reduce the effort and to simplify the manufacturing process of micro-optical devices that traditionally have to be structured in glass surfaces. The transformation process of Medusa 82 into a glasslike material involves an e-beam exposure, a thermal treatment, or a combination of both. Moreover, the adjustable contrast and sensitivity enable grayscale lithography. Different e-beam exposures trigger a different cross-linking degree within the layer, resulting in height variations after development. A postexposure bake step induces further cross-linking and a complete conversion into silicon oxide.

Multinuclear Tin-Based Macrocyclic Organometallic Resist for EUV Photolithography

“…The stability of a photoresist is an important issue for industrial applications. For example, the good-performing photoresist of HSQ has shown poor storage stability (5 °C storage, 6 months), hindering its practical application. , To test the storage stability, we left the TTC photoresist solution in the air at room temperature for over 6 months, without light shielding. 1 H NMR spectroscopic analysis indicates no change in the 1 H NMR spectrum (Figure S8), indicating good storage stability.…”