Catalyst-free combined synthesis of Zn/ZnO core/shell hollow microspheres and metallic Zn microparticles by thermal evaporation and condensation route

Here we report catalyst-free combined synthesis of metal/semiconductor Zn/ZnO core/shell microspheres with hollow interiors on Si substrate and metallic Zn polygonal microparticles on glass substrate in a single experiment via thermal evaporation and condensation technique using nitrogen (N2) as carrier agent at 800 °C for 120 min. The Zn/ZnO hollow microspheres were observed to have dimensions in the range of 70–80 μm whereas metallic Zn microparticles with polygonal cross section and oblate spherical shape were found to be of 8–10 μm. Some of the Zn/ZnO core/shell hollow spheres were also observed to have single crystalline ZnO pointed rods in extremely low density grown on the outer shell. The structural, compositional and morphological characterization of the products obtained on the substrates were performed by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and selected area electron diffraction (SAED). A vapor–liquid–solid (VLS) process based growth mechanism was proposed for the formation of Zn/ZnO core/shell microspheres with hollow interior. The optical properties of Zn/ZnO core/shell microspheres were investigated by measuring the photoluminescence (PL) spectra at room temperature (RT). Two very strong emission bands were observed at 373 and 469 nm in the ultraviolet and visible regions respectively under excitation wavelength of 325 nm. Also the effect of the various excitation wavelengths on the PL behaviour was studied at room temperature. PL studies of Zn/ZnO core/shell microspheres show the promise of the material for applications in UV and blue light optical devices.

Research highlights▶ Catalyst-free combined synthesis of metal/semiconductor Zn/ZnO core/shell microspheres with hollow interiors on Si substrate and metallic Zn polygonal microparticles on glass substrate in a single experiment via thermal evaporation and condensation technique was reported. The Zn/ZnO hollow microspheres were observed to have dimensions in the range of 70–80 μm whereas metallic Zn microparticles with polygonal cross section and oblate spherical shape were found to be of 8–10 μm. Some of the Zn/ZnO core/shell hollow spheres were also observed to have single crystalline ZnO pointed rods in extremely low density grown on the outer shell. A vapor–liquid–solid (VLS) process based growth mechanism was proposed for the formation of Zn/ZnO core/shell microspheres with hollow interior. The optical properties of Zn/ZnO core/shell microspheres were investigated by measuring the photoluminescence (PL) spectra at room temperature (RT). Two very strong emission bands were observed at 373 and 469 nm in the ultraviolet and visible regions respectively under excitation wavelength of 325 nm. Also the effect of the various excitation wavelengths on the PL behaviour was studied at room temperature. PL studies of Zn/ZnO core/shell microspheres show the promise of the material for applications in UV and blue light optical devices.