Growth and Photoelectrochemical Characterization of Epitaxial ZnTe Photocathodes for Carbon Dioxide Reduction

Abstract

Harnessing solar energy to drive photocatalytic carbon dioxide reduction reactions (CO 2 RR) provides an appealing pathway to generate hydrocarbon and oxygenated fuels without an external power source. Zinc telluride (ZnTe) is a II-VI semiconductor which has been identified as a promising photocathode material due to its suitable band gap alignments to CO 2 reduction reaction potentials, chemical stability, and strong p-type character. Using molecular beam epitaxy (MBE), single crystal and epitaxial layers are synthesized to gain a deeper understanding of fundamental charge transport and reactivity mechanisms between the single crystal ZnTe thin film and the CO 2 -saturated electrolyte. These findings are of fundamental interest and are also critical to the design of efficient tandem solar fuels generators for unassisted photoelectrochemical CO 2 R. Epitaxy allows for highly controlled doping of the thin films over a large range of carrier concentrations. This work focuses largely on the synthesis and characterization of nitrogen doped p-type ZnTe via MBE. Films grown in the temperature range of 340–360ºC on GaAs of (100) orientation with a 200 nm undoped ZnTe buffer layer and a 100 nm doped ZnTe layer have been characterized by RHEED, XRD, AFM, and Hall effect measurements. Doping concentrations between 10 20 cm -3 and 10 18 cm -3 have been achieved. Dark current-voltage measurements have been used to indicate stability of the electrode in aqueous conditions in less than -0.5 V vs RHE. Future work will include further investigations into carrier dynamics via transient absorption spectroscopy and continual development of a tandem, ZnTe-based photocathode.