Spectral and luminescent properties of ZnO–SiO2 core–shell nanoparticles with size-selected ZnO cores

Abstract

Deposition of silica shells onto ZnO nanoparticles (NPs) in dimethyl sulfoxide was found to be an efficient tool for terminating the growth of ZnO NPs during thermal treatment and producing stable core–shell ZnO NPs with core sizes of 3.5–5.8 nm. The core–shell ZnO–SiO₂ NPs emit two photoluminescence (PL) bands centred at ∼370 and ∼550 nm originating from the direct radiative electron–hole recombination and defect-mediated electron–hole recombination, respectively. An increase of the ZnO NP size from 3.5 to 5.8 nm is accompanied by a decrease of the intensity of the defect PL band and growth of its radiative life-time from 0.78 to 1.49 μs. FTIR spectroscopy reveals no size dependence of the FTIR-active spectral features of ZnO–SiO₂ NPs in the ZnO core size range of 3.5–5.8 nm, while in the Raman spectra a shift of the LO frequency from 577 cm⁻¹ for the 3.5 nm ZnO core to 573 cm⁻¹ for the 5.8 nm core is observed, which can indicate a larger compressive stress in smaller ZnO cores induced by the SiO₂ shell. Simultaneous hydrolysis of zinc(II) acetate and tetraethyl orthosilicate also results in the formation of ZnO–SiO₂ NPs with the ZnO core size varying from 3.1 to 3.8 nm. However, unlike the case of the SiO₂ shell deposition onto the pre-formed ZnO NPs, individual core–shell NPs are not formed but loosely aggregated constellations of ZnO–SiO₂ NPs with a size of 20–30 nm are. The variation of the synthetic procedures in the latter method proposed here allows the size of both the ZnO core and SiO₂ host particles to be tuned.