Additive manufacture of complex 3D Au-containing nanocomposites by simultaneous two-photon polymerisation and photoreduction

The fabrication of complex three-dimensional gold-containing nanocomposite structures by simultaneous two-photon polymerisation and photoreduction is demonstrated. Increased salt delivers reduced feature sizes down to line widths as small as 78 nm, a level of structural intricacy that represents a significant advance in fabrication complexity. The development of a general methodology to efficiently mix pentaerythritol triacrylate (PETA) with gold chloride hydrate (HAuCl4 center dot 3H(2)O) is reported, where the gold salt concentration is adjustable on demand from zero to 20 wt%. For the first-time 7-Diethylamino-3-thenoylcoumarin (DETC) is used as the photoinitiator. Only 0.5 wt% of DETC was required to promote both polymerisation and photoreduction of up to 20 wt% of gold salt. This efficiency is the highest reported for Au-containing composite fabrication by two-photon lithography. Transmission Electron Microscopy (TEM) analysis confirmed the presence of small metallic nanoparticles (5.4 +/- 1.4 nm for long axis / 3.7 +/- 0.9 nm for short axis) embedded within the polymer matrix, whilst X-ray Photoelectron Spectroscopy (XPS) confirmed that they exist in the zero valent oxidation state. UV-vis spectroscopy defined that they exhibit the property of localised surface plasmon resonance (LSPR). The capability demonstrated in this study opens up new avenues for a range of applications, including plasmonics, metamaterials, flexible electronics and biosensors.