Omnidirectional Printing of PEDOT:PSS for High-Conductivity Spanning Structures

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), a prominent conducting polymer, holds significance in both industry and academia. However, prevailing fabrication techniques struggle to build spanning features of PEDOT:PSS with both high electrical conductivity and fine resolution due to layerwise assembly in the xy plane. Here, we report an "omnidirectional printing and secondary doping" strategy to construct spanning, filamentary and out-of-plane 3D PEDOT:PSS with high conductivity. The pristine PEDOT:PSS suspension is homogeneously concentrated to form a printable ink with high solids (∼15 wt %) consisting of entangled PEDOT:PSS nanofibrils. Such ink shows a high storage modulus G' (43531 Pa) and a high yield stress τ_y (4325 Pa), thereby enabling omnidirectional printing. Secondary doping with sulfuric acid or other polar solvents is used to induce a synergetic process of PSS loss, conformational change, phase separation, and crystallinity enhancement in the printed structures, resulting in a remarkable enhancement of conductivity in dehydrated (65,378 S/m) and swollen (7190 S/m) states. As a proof-of-concept, 2D grids with a feature size of 15 μm and 3D overhanging arches are fabricated for high-performance transparent glass heaters and 3D interconnection, respectively. This work promises great potential for the development of advanced flexible electronics, wearable devices, and bioelectronics.