Issue 41, 2020

Atomically tunable photo-assisted electrochemical oxidation process design for the decoration of ultimate-thin CuO on Cu2O photocathodes and their enhanced photoelectrochemical performances

Abstract

A representative method of forming CuO thin films on Cu2O photoabsorbers is simple annealing oxidation at high temperature in a controlled oxygen atmosphere, but the typical oxidation process is very quick and irregular, resulting in a high density of defect sites. To maximize the beneficial effect of CuO/Cu2O heterojunction photocathodes, novel criteria for CuO preparation have been suggested: (1) in-plane epitaxy with Cu2O, (2) atomic layer-by-layer growth, (3) ultimate-thin and completely conformal coating, and (4) minimized internal defects. As a novel strategy to achieve these criteria, we propose a photo-assisted electrochemical oxidation (PAEO) method, where the Cu2O surface is precisely phase-changed into the ultimate-thin CuO layer with a thickness of 4 nm via fine thickness control using photoenergy and an external potential at room temperature. The produced CuO crystals are grown on Cu2O without generating structural defects by accommodating the epitaxial relationship below the critical thickness. From static and dynamic (photo)electrochemical analyses, the decoration of ultimate-thin CuO offers high electrical conductivity and fast charge transport, guarantees sufficient open-circuit potential (OCP), and substantially retains the initial OCP value by minimizing the contribution of recombination loss. Finally, the PAEO-treated photocathodes exhibit an excellent photocurrent density of 15 mA cm−2 (approaching the theoretical maximum current) and 8.3 mA cm−2 at 0 V vs. RHE in electrolytes with and without scavenger hydrogen peroxide (H2O2), respectively, as well as a OCP of 0.78 V, even with the use of suboptimal Al-doped ZnO buffer layers.

Graphical abstract: Atomically tunable photo-assisted electrochemical oxidation process design for the decoration of ultimate-thin CuO on Cu2O photocathodes and their enhanced photoelectrochemical performances

Supplementary files

Article information

Article type
Paper
Submitted
17 Jun 2020
Accepted
06 Oct 2020
First published
07 Oct 2020

J. Mater. Chem. A, 2020,8, 21744-21755

Atomically tunable photo-assisted electrochemical oxidation process design for the decoration of ultimate-thin CuO on Cu2O photocathodes and their enhanced photoelectrochemical performances

D. S. Kim, Y. B. Kim, S. H. Jung, N. G. Deshpande, J. H. Choi, H. S. Lee and H. K. Cho, J. Mater. Chem. A, 2020, 8, 21744 DOI: 10.1039/D0TA06010K

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