Published online by Cambridge University Press: 10 April 2013
Two-photon fabrication is a powerful method of fabricating complex microstructures. Superresolution by methods analogous to stimulated emission depletion (STED) has been described previously, enabling sub-100 nm imaging with 800 nm light. STED-related methods of enhancing imaging resolution require photoresists with exposure conditions for which the photoresist exhibits negative contrast, i.e., image density decreases with increasing exposure from the depletion beam. We have observed decreasing voxel size with increasing exposure during two-photon initiated polymerization of acrylate- and methacrylate-based photoresists, that is, negative imaging contrast, γ < 0, independent of the type of photoinitiator. Negative contrast is not observed in epoxy-type photoresists containing photoacid generators. An investigation of the exposure conditions has led us to conclude that radical-radical recombination at high exposure is responsible for negative contrast. Results of the investigation, discussion of the proposed mechanism for negative contrast and implications for two-photon superresolution will be presented.