Design of hybrid sol-gel films for direct x-ray and electron beam nanopatterning

New epoxy based sol-gel organic inorganic materials, showing lithographic resist-like properties without the addition of any photocatalysts, are presented. To obtain a material sensitive to radiation, specific sol-gel syntheses based on an organically modified alkoxide containing an epoxy ring, 3-glycidoxypropyltrimethoxysilane (GPTMS), have been developed. The synthesis and the patternability of hybrid materials have been obtained controlling the inorganic crosslinking degree and with an almost total absence of organic polymerization. Two examples of directly patternable hybrid films, called GB and GGe, have been synthesized using acidic (GGe) and basic (GB) conditions and obtaining different compositions. After electron beam lithography (EBL) or x-ray synchrotron radiation lithography (XRL) the polymerization of the organic component of the sol-gel film occurs, generating a hardening of the structure after post-exposure baking. The exposed polymerized material becomes insoluble, determining a negative resist-like behaviour of the film: the lithographic process of nanopatterning results from the dissolution of the unexposed areas in proper solvents (developers). Spatial resolution of the order of 200?nm is reported and a contrast of 2.2 is achieved. The novelty of this work is that epoxy based materials, which have enhanced thermomechanical stability with respect to the more usual acrylic based resins, are directly nanopatterned for the first time by electron beam (EB) and/or x-ray beam radiation exposure without the aid of catalysts for polymerization. In contrast to common resists that are sacrificial layers of the fabrication process, direct patternable sol-gel hybrids constitute the final material of the devices. In fact, an example of doping with a light emitting dye is reported together with the achievement of directly patterned structures by EBL and XRL.