Fabrication of PEDOT Nanocone Arrays with Electrochemically Modulated Broadband Antireflective Properties

Ordered nanocone arrays of the electroactive polymer poly­(3,4-ethylenedioxythiophene) (PEDOT) were fabricated by the simultaneous oxygen plasma etching of an electrodeposited PEDOT thin film coated with a hexagonally closed packed polystyrene bead monolayer. PEDOT nanocone arrays with an intercone spacing of 200 nm and an average nanocone height of 350 nm exhibited a low broadband reflectivity of <1.5% from 550 to 800 nm. Electrochemical modulation of the oxidation state of the PEDOT nanocone array film was used to change both its ex situ absorption spectrum (electrochromism) and reflection spectrum (electroreflectivity). The sign of the PEDOT nanocone array electroreflectivity was opposite to that observed from unmodified PEDOT thin films; this significant difference is attributed to the unique optical behavior of nanostructured surfaces with an interfacial layer that contains a graded mix of air and highly absorptive nanocones. The combined electrochromic and electroreflective behavior of the antireflective PEDOT nanocone array films should find promising applications in solar energy cells, sensors and other optical devices.