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Progress in Chemistry 2020, Vol. 32 Issue (9): 1368-1375 DOI: 10.7536/PC200123 Previous Articles   Next Articles

• Review •

Thin Film Protection Strategy of Ⅲ-Ⅴ Semiconductor Photoelectrode for Water Splitting

Xuqiang Zhang1, Gongxuan Lu1,*()   

  1. 1. State Key Laboratory for Oxo Synthesis and Selective Oxidation,Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China
  • Received: Revised: Online: Published:
  • Contact: Gongxuan Lu
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Due to high radiation resistance, good temperature characteristics and stability at high temperature, photoelectrodes integrated by Ⅲ-Ⅴ semiconductor materials, such as GaAs, GaP and InP, show higher solar absorption efficiency and photoelectric conversion efficiency compared with photoelectrodes constructed from other materials. However, the physical and chemical properties of most Ⅲ-Ⅴ semiconductors in aqueous electrolytes are very unstable, resulting in a rapid degradation of solar-driven water splitting performance. The recent progress of protective layer films research in improving the electrochemical stability of Ⅲ-Ⅴ semiconductor photoelectrodes are reviewed. In order to obtain a stable and efficient photoelectric reaction interface and the water splitting efficiency, the reasons of material attenuation and corresponding improvement methods have been highlighted. In addition, the future development of thin-layer protection strategies to obtain more efficient solar-driven water splitting devices based on Ⅲ-Ⅴ semiconductors have been prospected.

Contents

1 Introduction

2 Mechanisms of corrosion of Ⅲ-Ⅴ group semiconductors and protective measures

3 Protection of photocathode of Ⅲ-Ⅴ group semiconductors in solar-driven water splitting

4 Protection of photoanode in solar-driven water splitting

5 Conclusion

Key words: Ⅲ-Ⅴ semiconductor materials, photoelectrode, water splitting, protective layer films
Fig.1 Schematic illustration of the energy band diagrams of semiconductor photoelectrodes for solar water splitting:(a) single-photon route;(b) two-photon route;(c) multi-photon route[9]
Fig.2 Schematic diagram for blende crystal structure of GaAs[10]
Fig.3 (a) Stable and(b) unstable band alignment for semiconductor electrodes,where n E decomp and p E decomp are cathodic decomposition potential and anodic decomposition potential[17]
Table 1 The performance of Ⅲ-Ⅴ semiconductor photoelectrodes with protection layer protects for hydrogen evolution performance
Photocathode Protection layer Preparation method of protection layer Stability(h) J(mA/cm2) E vs RHE(V) ref
p-InP “thin oxide” acid etching 1 week — 0.54 32
p-Cu(In,Ga)Se2 n-CdS CB 16 9 0.5 33
p-InP TiO2 ALD 4 35 0.73 34
p-InP TiO2 ALD 2 24 0.80 35
p-GaAs TiO2 CVD — — — 36
GaAs TiO2 ALD — — 0.5 37
GaAs Polyimide Print 8 day 23.1 1.022 38
np-GaAs SrTiO3 MBE 24 6 0.94 39
GaAs/InGaP TiO2 ALD 40 8.5 2.25 40
GaInP2/GaAs/Ge GaN MBE 80 10.3 2.2 41
GaInP/GaInAs TiO2/AlInP CB 50 15.7 0.6 42
Fig.4 SEM image of the InP nanoarrays coated with dense TiO2 film;(b) J-E data for TiO2/InP[34]
Fig.5 (a) Cross-section of an integrated GaAs photocathode fabricated by printing-assembly method;(b) Current density-time(J-t) plots of integrated GaAs photocathodes[38]
Fig.6 (a) Scheme of SrTiO3/np-GaAs(001) photocathode with the 16 nm-thick protection layer.(b) The high-angle annular dark-field imaging and interface atomic structure of the SrTiO3/np-GaAs(001).(c) The corresponding energy alignment at the water/SrTiO3 on SrTiO3/GaAs(001) interfaces.(d) The XPS valence band offset at the SrTiO3/n-GaAs(001) interface[39]
Fig.7 (a) Cross-sectional SEM image of a GaAs/InGaP/TiO2/Ni 2 J structural photoelectrode[40].(b) Schematic illustration of the 3 J structural GaN-GaInP2/GaAs/Ge protected by multifunctional GaN nanostructures[41]
Fig.8 Schematic structure and an expected band diagram of the n-Si/p-CuI/nip a-Si/np GaP/RuO2 electrode [53]
Table 2 The oxygen evolution performance of Ⅲ-Ⅴ semiconductors(such as GaAs, InP, GaP, GaInP2, GaAlAs) with protection layers
Photoanode Protection layer Preparation method of protection layer Stability(h) J(mA/cm2) E vs OER(V) ref
n-GaP Au evaporation — — 0.05 46
n-GaP Ag sputter — — -1.23 47
p-GaInP2 — — 10 35 — 48
n-GaAs, n-GaAlAs Al2O3, TiO2 sputtering — — — 49
n-GaAs Pd/MnOx CB 80 min 11 -0.86 50
n-GaAs ITO sputtering — — — 51
n-GaN NiO spin coating 110 0.5 — 52
n-GaP TiO2/NiOx ALD/e-beam 5 2.5 -0.35 29
np +-GaAs TiO2 ALD/e-beam 25 14 -0.57 29
Fig.9 (a) Cross-sectional scheme of a stable photoanode against corrosion.(b) The photocurrent density of 2 nm Ni/118 nm TiO2-coated np +-GaAs and n-GaP photoelectrodes[29]
Fig.10 Scheme of p-GaAs(100) modified with surface dipoles[56]
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