We have previously demonstrated that two-photon induced polymerization allows fabrication of complex threedimensional structures such as photonic crystals and micromachines with a spatial resolution around 120 nm. In this report, we show the resolution improvement till 65 nm. Experimentally, 780-nm femtosecond laser pulses were focused into a photopolymerizable resin by a high numerical aperture objective lens. The resin is polymerized by means of radical initiation. In the radical polymerization, oxygen molecules dissolved in the resin inhibit the polymerization reactions by scavenging the radicals that initiate the polymerization. At controlled laser pulse energy, the radicals can survive and initiate polymerization only at the region where exposure energy is larger than the polymerization threshold, leading to a sub-diffraction-limited spatial resolution. In order to further improve the fabrication accuracy, we introduced a radical quencher into the resin, and at an optimized concentration the lateral spatial resolution was improved to 100 nm. Moreover, we fabricated a suspended fiber connected between two anchors by controlling the exposure dose within the fiber. After removing the unsolidified resin by ethanol and drying, a 65-nm width fiber was obtained, suggesting a possible spatial resolution of similar dimension. The size less than 1/10 of the excitation wavelength could satisfy requirements of many photonic and optoelectronic devices.
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