Additive Manufacturing of 3D-Architected Multifunctional Metal Oxides

Additive manufacturing (AM) of complex three-dimensional (3D) metal oxides at the micro- and nanoscales has attracted considerable attention in recent years. State-of-the-art techniques that use slurry-based or organic-inorganic photoresins are often hampered by challenges in resin preparation and synthesis, and/or by the limited resolution of patterned features. A facile process for fabricating 3D-architected metal oxides via the use of an aqueous metal-ion-containing photoresin is presented. The efficacy of this process, which is termed photopolymer complex synthesis, is demonstrated by creating nanoarchitected zinc oxide (ZnO) architectures with feature sizes of 250 nm, by first patterning a zinc-ion-containing aqueous photoresin using two-photon lithography and subsequently calcining them at 500 oC. Transmission electron microscopy (TEM) analysis reveals their microstructure to be nanocrystalline ZnO with grain sizes of 5.1 +/- 1.6 nm. In situ compression experiments conducted in a scanning electron microscope show an emergent electromechanical response: a 200 nm mechanical compression of an architected ZnO structure results in a voltage drop of 0.52 mV. This photopolymer complex synthesis provides a pathway to easily create arbitrarily shaped 3D metal oxides that could enable previously impossible devices and smart materials.