Fabrication of polyhedral CdS flower-like architectures have been achieved on a large scale through a mixed solvothermal method. The obtained CdS are characterized by X-ray diffraction, field-emission scanning electron microscopy and transmission electron microscopy, and the results indicate that the CdS flower-like architectures with diameters of 1.5–2.0 µm are hexagonal wurtzite phase and are assembled by some pyramids with the bottom side length of about 440 nm, which have some crystallographic faces. A series of relevant experiments through altering experimental parameters, indicate that the temperature, starting materials and solvent play key roles for the shape evolution of CdS flower-like architectures. The studies of optical properties for polyhedral CdS flower-like architectures indicate that the UV-vis spectroscopy shows a blue-shift absorption peak at 500 nm compared to that of bulk CdS, the photoluminescence spectroscopy shows an emission peak at 640 nm and another strong emission peak at 695 nm, which are believed to be attributed to excitonic emission and deep levels. <alternatives> [...] </alternatives>
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