Quantum size effect on ZnO nanoparticle-based discs synthesized by mechanical milling

Zinc oxide (ZnO) nanoparticles ranging ∼7–15 nm in size were successfully synthesized by the ball-milling technique. Mechanical milling was found very functional in producing ZnO nanoparticles with the possibility of obtaining large quantities. The milled nanoparticles were compared with commercial ZnO nanopowder. High-resolution scanning electron microscopy and atomic force microscopy analyses revealed a reduction in the lattice space and grain size with increased milling time, as well as severe lattice deformations in some of the nanoparticles. The milling process also had a significant effect on the grain crystallinity as illustrated by decreased lattice strain based on the X-ray diffraction lattice constant and full-wave at half-maximum data. The photoluminescence (PL) spectra of the ZnO powder showed a UV emission band at 380 nm with a visible PL emission in the green band peaking at 535 nm. The relative intensities of these peaks drastically changed with increased milling time due to the size quantization effect and surface defects (oxygen vacancies and zinc/oxygen interstitials) in the ZnO nanopowder. The Raman spectra of the ZnO powder indicated eight sets of optical phonon modes at the Γ point of the Brillouin zone, which red shifted and broadened with increased milling time. As the milling proceeded, clearly reduced grain size, homogenization, and other properties were observed.