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Crystal orientation-dependent etching and trapping in thermally-oxidised Cu<sub>2</sub>O photocathodes for water splitting


Niu, Wenzhe; Moehl, Thomas; Adams, Pardis; Zhang, Xi; Lefèvre, Robin; Cruz, Aluizio M; Zeng, Peng; Kunze, Karsten; Yang, Wooseok; Tilley, S David (2022). Crystal orientation-dependent etching and trapping in thermally-oxidised Cu<sub>2</sub>O photocathodes for water splitting. Energy & Environmental Science, 15(5):2002-2010.

Abstract

Ammonia solution etching was carried out on thermally-oxidised cuprous oxide (TO-Cu2O) in photocathode devices for water splitting. The etched devices showed increased photoelectrochemical (PEC) performance compared to the unetched ones as well as improved reproducibility. -8.6 mA cm-2 and -7 mA cm-2 photocurrent density were achieved at 0 V and 0.5 V versus the reversible hydrogen electrode (VRHE), respectively, in the champion sample with an onset potential of 0.92 VRHE and a fill factor of 44 %. An applied bias photon-to-current efficiency of 3.6 % at 0.56 VRHE was obtained, which represents a new record for Cu2O-based photocathode systems. Capacitance-based profiling studies showed a strong pinning effect from interfacial traps in the as-grown device, and these traps were removed by ammonia solution etching. Moreover, the etching procedure gave rise to a diverse morphology of Cu2O crystals based on the different crystallographic orientations. The distribution of crystallographic orientations and the relationship between the crystal orientation and the morphology after etching were examined by electron backscatter diffraction (EBSD) and scanning electron microscopy (SEM). The high-index crystal group showed a statistically higher PEC performance than the low-index group. X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) revealed metallic copper at the Cu2O/Ga2O3 interface, which we attribute as the dominant trap that limits the PEC performance. It is concluded that the metallic copper originates from the reduction of the CuO impurity layer on the as-grown Cu2O sample during the ALD process, while the reduction from Cu2O to Cu is not favorable.

Abstract

Ammonia solution etching was carried out on thermally-oxidised cuprous oxide (TO-Cu2O) in photocathode devices for water splitting. The etched devices showed increased photoelectrochemical (PEC) performance compared to the unetched ones as well as improved reproducibility. -8.6 mA cm-2 and -7 mA cm-2 photocurrent density were achieved at 0 V and 0.5 V versus the reversible hydrogen electrode (VRHE), respectively, in the champion sample with an onset potential of 0.92 VRHE and a fill factor of 44 %. An applied bias photon-to-current efficiency of 3.6 % at 0.56 VRHE was obtained, which represents a new record for Cu2O-based photocathode systems. Capacitance-based profiling studies showed a strong pinning effect from interfacial traps in the as-grown device, and these traps were removed by ammonia solution etching. Moreover, the etching procedure gave rise to a diverse morphology of Cu2O crystals based on the different crystallographic orientations. The distribution of crystallographic orientations and the relationship between the crystal orientation and the morphology after etching were examined by electron backscatter diffraction (EBSD) and scanning electron microscopy (SEM). The high-index crystal group showed a statistically higher PEC performance than the low-index group. X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) revealed metallic copper at the Cu2O/Ga2O3 interface, which we attribute as the dominant trap that limits the PEC performance. It is concluded that the metallic copper originates from the reduction of the CuO impurity layer on the as-grown Cu2O sample during the ALD process, while the reduction from Cu2O to Cu is not favorable.

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Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
08 Research Priority Programs > Solar Light to Chemical Energy Conversion
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Environmental Chemistry
Physical Sciences > Renewable Energy, Sustainability and the Environment
Physical Sciences > Nuclear Energy and Engineering
Physical Sciences > Pollution
Uncontrolled Keywords:Pollution, Nuclear Energy and Engineering, Renewable Energy, Sustainability and the Environment, Environmental Chemistry
Language:English
Date:1 January 2022
Deposited On:31 Mar 2022 06:28
Last Modified:28 Jan 2024 02:46
Publisher:Royal Society of Chemistry
ISSN:1754-5706
OA Status:Hybrid
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1039/d1ee03696c
Project Information:
  • : FunderSNSF
  • : Grant ID200020_184737
  • : Project TitlePhotoelectrochemical Synthesis of Hydrogen and Value-Added Chemicals for a Sustainable Chemical Industry
  • Content: Accepted Version
  • Licence: Creative Commons: Attribution 4.0 International (CC BY 4.0)