ZnO/CdS core/shell nanorod arrays were fabricated by a two-step method. Single-crystalline ZnO nanorod arrays were first electrochemically grown on SnO(2):F (FTO) glass substrates. Then, CdS nanocrystals were deposited onto the ZnO nanorods, using the successive ion layer adsorption and reaction (SILAR) technique, to form core/shell nanocable architectures. Structural, morphological and optical properties of the nanorod heterojunctions were investigated. The results indicate that CdS single-crystalline domains with a mean diameter of about 7 nm are uniformly and conformally covered on the surface of the single-crystalline ZnO nanorods. ZnO absorption with a bandgap energy value of 3.30 ± 0.02 eV is present in all optical transmittance spectra. Another absorption edge close to 500 nm corresponding to CdS with bandgap energy values between 2.43 and 2.59 eV is observed. The dispersion in this value may originate in quantum confinement inside the nanocrystalline material. The appearance of both edges corresponds with the separation of ZnO and CdS phases and reveals the absorption increase due to CdS sensitizer. The photovoltaic performance of the resulting ZnO/CdS core/shell nanorod arrays has been investigated as solar cell photoanodes in a photoelectrochemical cell under white illumination. In comparison with bare ZnO nanorod arrays, a 13-fold enhancement in photoactivity was observed using the ZnO/CdS coaxial heterostructures.
CdS quantum dots (QDs) decorated ZnO nanorod (NR) arrays were fabricated by a two-step method. The first step consisted in electrochemical growth of single-crystalline ZnO NR arrays, followed by the novel spin-coating assisted SILAR method for decorating the ZnO NRs with CdS QDs. Structural, morphological and optical characterization of CdS QDs/ZnO NR arrays were done. ZnO NRs had a single crystal wurtzite structure growing along the c-axis. The decorated CdS QDs had a quasi-spherical shape with a mean diameter of about 5 nm. The increase of CdS content produces an increase in the visible part of the absorption spectrum. Bandgap energy values for ZnO between 3.26–3.29 eV were obtained. For CdS the measured absorption edge values are between 2.35–2.65 eV (decreasing with the number of coating cycles). Numerical simulations based on effective medium approximation were done to verify these features. The Urbach tail parameter in CdS absorption edge is between 44–52 meV. The photovoltaic performance of ZnO and CdS QDs/ZnO NRs have been evaluated in a photoelectrochemical solar cell configuration with a polysulfide electrolyte under white illumination. The decoration of ZnO NRs with CdS QDs leads to a cell performance of JSC = 2.67 mA/cm2, VOC = 0.74 V, FF = 0.30 and η = 1.48%.
Texture characterization in thin films from standard powder x-ray diffraction (XRD) rely on the comparison between observed peak relative intensities with those of powder diffraction standards of the same compound, trough the so-called texture coefficient (TC). While these methods apply for polycrystalline materials with isotropic grains, they are less accurate—and even wrong—for anisotropic materials like ZnO oriented single-crystal nano-rods, which would require the use of dedicated XRD texture setups. By using simple geometrical considerations, we succeed in discriminating between texture and morphology contributions to the observed intensity ratios in powder diffraction patterns. On this basis, we developed a method that provides a quantitative determination of both texture (polar distribution) and morphology (aspect ratio of nano-rods), using simple x-ray powder diffraction. The method is illustrated on a typical sample from a series of Zinc oxide (ZnO) nano-rod arrays grown onto a gold thin film sputtered onto a F:SnO2-coated glass substrate (FTO) by using cathodic electro-deposition. In order to check the consistency of our method, we confronted our findings with scanning electron microscope (SEM) images, grazing incidence diffraction (GID), and XRD pole-figures of the same sample. Nevertheless, the proposed method is self-consistent and only requires the use of a standard powder diffractometer, nowadays available in most solid-state laboratories.
Vertically aligned ZnO/Cu2O heterostructure nanopillar arrays consisting of a ZnO core and a Cu2O shell were fabricated by a two-step electrochemical deposition method. Morphological, structural and optical properties of the nanopillar heterojunctions were investigated. The surface of the single-crystalline ZnO nanopillars was coated uniformly, conformally and densely over the entire nanopillar length by numerous Cu2O nanocrystals (25–35 nm mean diameter), constituting a conformal shell layer 90 nm thick, integrating these two materials into an electronically intimate composite. The optical properties can be interpreted, by appropriate fittings of each feature, as being due to the properties of the bare ZnO nanopillar array plus the increased absorption of Cu2O. This study demonstrates that electrodeposition is a suitable and accessible technique for large-scale fabrication of nanopillar heterostructures and to achieve conformal coverage of nanostructured samples.
The optical properties of bare ZnO nanorods and sensitized nanostructures, with Cu 2 O and CdS, are comparatively studied. These nanostructures may show improved photovoltaic performance compared to planar ones. ZnO nanorod arrays were grown by electrochemical deposition. In a second step, Cu 2 O was also deposited electrochemically, while for CdS successive ion layer adsorption and reaction techniques were used. The experimental results are interpreted using numerical simulation based on an effective medium theory. Bare nanorod samples reveal mainly the direct ultraviolet absorption edge of ZnO (between 3.25 and 3.30 eV) and a monotonically increasing transmittance from the ultraviolet into the red. This increase is originated in light scattering, probably by the nanometric structure of the samples. For the sensitized samples reduced transmittance in the solar spectrum region is observed and several well-defined absorption edges appear. Spectral absorption edge shifts are interpreted comparing with numerical simulations. For CdS the measured shifts are larger than the ones obtained from numerical simulations. The difference may be due to the combined influence of sub-bandgap absorption, light scattering in the nanorod array and quantum confinement in the nanocrystalline structure of sensitizer layers. For Cu 2 O its more complex electronic structure gives larger dispersion in the results although major absorption edges are clearly observed.
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