NDLI: Optical, electronic, and photoelectrochemical properties of the p-type Cu3−xVO4 semiconductor

Content Provider	Royal Society of Chemistry (RSC)
Author	Maggard, Paul A. Sahoo, Prangya P. Zoellner, Brandon
Copyright Year	2015
Abstract	Investigations into new p-type metal oxides with small bandgap sizes, i.e., Eg ∼0.9 eV to ∼1.5 eV, are currently needed to enable the preparation of tandem cells with high solar-to-hydrogen conversion efficiencies. The p-type Cu(I)-vanadate, Cu3VO4 (space group I2m (no. 121), Z = 2, a = 4.581(4) Å, c = 8.998(2) Å), was synthesized in high purity using solid-state methods and investigated for its small optical bandgap size (Eg ∼ 1.2 eV) and photoelectrochemical properties in the form of polycrystalline films. Powder X-ray diffraction and electron microscopy data show that, beginning at 300 °C in air, a Cu-deficient composition is formed according to: Cu3VO4(s) + (x/2) O2(g) → Cu3−xVO4(s) + x CuO(s). At 350 °C the compound decomposes at the surfaces into the Cu(II)-containing oxides CuO and Cu3V2O8 (3 : 1 molar ratio), the latter protruding as rods (i.e., ∼15–25 nm in width by ∼1–5 μm in length) from the particles' surfaces. Polycrystalline films of p-type Cu3VO4 were prepared under these conditions (i.e., heated in air at 300 °C or 350 °C) and found to yield significant cathodic photocurrents under solar-simulated, visible-light irradiation (λ > 420 nm; AM 1.5 G filter, irradiant power density of ∼100 mW cm−2). Their photocurrents increased with the heating temperature of the film and with the applied bias, e.g., ∼0.1 mA cm−2 at zero applied bias to ∼0.25 mA cm−2 at −0.2 applied bias (pH = 5.8). The photocurrent of a non-heated film was negligible compared to the films heated in air and exhibited a larger dark current. Further, when CuO nanoparticles were formed directly onto the Cu3VO4 films from aqueous Cu(NO3)2 solutions (i.e., 0.1 M and 0.25 M), cathodic photocurrents of ∼0.2 mA cm−2 are similarly found. Mott–Schottky measurements determined the energetic potential of the Cu3VO4 conduction band to be at ∼−0.63 V versus RHE at pH = 5.8, with an acceptor concentration of ∼1.29 × 1017 cm−3. Thus, a type-II band offset is predicted to occur between the p-type Cu3VO4 film and the p-type CuO surface nanoparticles, and elucidating the critical role of the CuO surface nanoparticles in forming a charge rectification barrier and enhancing the charge separation at the surfaces. Electronic structure calculations show that the conduction band states of Cu3VO4 are delocalized within the ab-plane of the structure and exhibit an ∼2 eV band dispersion centered around the gamma k-point. The bandgap size, conduction band dispersion, and band energies of Cu3VO4 are thus found to be promising for further investigations into tandem n-/p-type photoelectrochemical cells for solar energy conversion applications.
Starting Page	4501
Ending Page	4509
Page Count	9
File Format	HTM / HTML PDF
ISSN	20507488
Volume Number	3
Issue Number	8
Journal	Journal of Materials Chemistry A
DOI	10.1039/c4ta04876h
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	RHE Mott Extrinsic semiconductor Band gap Electronvolt Vanadate Space group Photoelectrochemical cell Crystallite X-ray crystallography Transmission electron microscopy Oxygen Copper(II) oxide Concentration Micrometre Amplitude modulation Irradiant (album) PH Photocurrent Photoreceptor cell Valence and conduction bands Critical Role Dispersion relation Construction point Solar energy
Content Type	Text
Resource Type	Article
Subject	Chemistry Renewable Energy, Sustainability and the Environment Materials Science

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