Photoelectrochemical and Raman characterization of nanocrystalline CdS grown on ZnO by successive ionic layer adsorption and reaction method

• Visible-light-sensitive ZnO/CdS heterostructures were prepared by SILAR.
• A large Raman peak width originates from a complex structure of CdS nanoparticles.
• Vibrational properties of CdS nanoparticles depend on SILAR cycle number.

Properties of CdS nanoparticles (NPs) grown by successive ionic layer adsorption and reaction (SILAR) method on the surface of electrodeposited ZnO films were studied by Raman, photocurrent and UV–Vis absorption spectroscopies. The CdS nanoparticles deposited at a SILAR cycle number (N) from 5 to 10 exhibit a broadening of the band gap (Eg) by 0.17–0.31 eV as compared with that of the CdS particles grown at N = 30. The size quantization of the interband transition energy in CdS nanoparticles is in accordance with the Raman spectroscopic data demonstrating a considerable increase in the LO peak intensity with increasing the N from 5 to 10 as a result of transition to resonant light scattering. The spectral width of the LO peak decreases from 50 to 15 cm− 1 as the N increases from 5 to 30 reflecting a less pronounced effect of the nanoparticle surface on the phonon scattering. A large spectral width of the Raman peaks is assumed to originate from a complex structure of the CdS nanoparticles comprising crystallinity domains that can affect the phonon confinement. The photocurrent spectroscopy of ZnO/CdS heterostructures showed that the band gap of CdS NPs deposited at N > 20 is smaller by ~ 0.08 eV than that of bulk cadmium sulfide. It was concluded that this effect is not associated with photoexcitation of structural defects but rather reflects intrinsic electronic properties of SILAR-deposited CdS nanoparticles.