Size-dependent photodegradation of CdS particles deposited onto TiO2 mesoporous films by SILAR method

The particle size, size distribution and photostability of CdS nanoparticles incorporated onto mesoporous TiO2 films by a successive ionic layer adsorption and reaction (SILAR) method were investigated by Raman spectroscopy, UV-Visible spectroscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). High-resolution TEM indicated that the synthesized CdS particles were hexagonal phase and the particle sizes were less than 5 nm for up to nine SILAR deposition cycles. Quantum size effect was found with the CdS-sensitized TiO2 films prepared with up to nine SILAR cycles. The band gap of CdS nanoparticles decreased from 2.65 to 2.37 eV with the increase of the SILAR cycles from 1 to 11. The investigation of the stability of the CdS/TiO2 films in air under illumination (440.6 mu W/cm(2)) showed that the photodegradation rate was up to 85 % per day for the sample prepared with three SILAR cycles. XPS analysis indicated that the photodegradation was due to the oxidation of CdS, leading to the transformation from sulphide to sulphate (CdSO4). Furthermore, the degradation rate was strongly dependent upon the particle size of CdS. Smaller particles showed faster degradation rate. The size-dependent photo-induced oxidization was rationalized with the variation of size-dependent distribution of surface atoms of CdS particles. Molecular dynamics-based theoretical calculation has indicated that the surface sulphide anion of a large CdS particle such as CdS made with 11 cycles (CdS x 11, average particle size = 5.6 nm) accounts for 9.6 % of the material whereas this value is increased to 19.2 % for (CdS x 3)-based smaller particles (average particle size = 2.7 nm). The photostability of CdS nanoparticles was significantly enhanced when coated with ZnS particles deposited with four SILAR cycles. The growth mechanism of ZnS upon CdS nanoparticles was discussed.