Facile fabrication of organic/inorganic nanotube heterojunction arrays for enhanced photoelectrochemical water splitting†
Abstract
Organic/inorganic heterojunction photoanodes are appealing for making concurrent use of the highly photoactive organic semiconductors, and the efficient dielectric screening provided by their inorganic counterparts. In the present work, organic/inorganic nanotube heterojunction arrays composed of TiO2 nanotube arrays and a semiconducting N,N-(dicyclohexyl) perylene-3,4,9,10-tetracarboxylic diimide (PDi) layer were fabricated for photoelectrochemical water splitting. In this arrayed architecture, a PDi layer with a tunable thickness was coated on anodic TiO2 nanotube arrays by physical vapor deposition, which is advantageous for the formation of a uniform layer and an adequate interface contact between PDi and TiO2. The obtained PDi/TiO2 junction exhibited broadened visible light absorption, and an effective interface for enhanced photogenerated electron–hole separation, which is supported by the reduced charge transfer resistance and prolonged excitation lifetime via impedance spectroscopy analysis and fluorescence emission decay investigations. Consequently, such a heterojunction photoanode was photoresponsive to a wide visible light region of 400–600 nm, and thus demonstrated a highly enhanced photocurrent density at 1.23 V vs. a reversible hydrogen electrode. Additionally, the durability of such a photoanode can be guaranteed after long-time illumination because of the geometrical restraint imposed by the PDi aggregates. These results pave the way to discover new organic/inorganic assemblies for high-performance photoelectric applications and device integration.