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Effective p-type photocurrent sensitization of n-Bi2O3 with p-CuBi2O4 and p-CuO: Z-scheme photoelectrochemical system


Nanostructured n-Bi2O3/p-CuBi2O4/p-CuO photocathodes with incident photon-to-current conversion efficiency IPCEmax = 70% (λ = 400 nm) have been prepared using electrochemical and chemical methods. Platelet-like BiOI nanocrystals electrochemically deposited on FTO substrate were used as precursors. CuI nanoparticles were deposited on the BiOI surface by successive ionic layer adsorption and reaction technique. Oxidative heat treatment of BiOI/CuI heterostructure in air leads to the formation of the Bi2O3/CuBi2O4/CuO composite. Binary oxide was formed as a result of solid-state interaction between bismuth and copper oxides at their interface.

Spectral sensitization of wide-gap n-Bi2O3 (band gap Eg = 2.80 eV) with narrow-gap p-CuBi2O4 (Eg = 1.80 eV) and p-CuO (Eg = 1.45 eV) extends spectral sensitivity range up to 800 nm by Z-scheme implementation: cathodic photocurrent is associated with the transition of photoelectrons from p-CuBi2O4 and p-CuO to the solution, while photoholes recombine with electrons of n-Bi2O3 conduction band. High quantum efficiency of photocurrent was achieved due to band-edge correlation in a three-component oxide heterostructure, combined with an internal electric field in p-CuBi2O4 and effective photon absorption by two narrow-band-gap p-CuBi2O4 and p-CuO semiconductors.

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This work was supported by project no. AP05130392 “Increasing of energy efficiency of photoelectrochemical solar cells due to application of new semiconductor materials” within the state program no. 217 “Development of Science” (the subprogram 102) of the Republic of Kazakhstan. We are grateful to Dr. Vidas Pakštas from the Center for Physical Sciences and Technology (Vilnius, Lithuania) and Yauhen Aniskevich (Belarusian State University) for their help in taking the SEM images.

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Correspondence to Eugene Streltsov.

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Dedicated to the memory of Ivo Alexandre Hümmelgen

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Malashchonak, М., Streltsov, E., Mazanik, A. et al. Effective p-type photocurrent sensitization of n-Bi2O3 with p-CuBi2O4 and p-CuO: Z-scheme photoelectrochemical system. J Solid State Electrochem 24, 401–409 (2020).

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  • Photoelectrochemistry
  • CuBi2O4
  • Photocurrent sensitization
  • Water splitting
  • Solar cells