Tuning the bandgap of 2D metallic Zn nanostructures

The semiconducting behavior of two-dimensional (2D) metal nanostructures has recently attracted much interest for their possible applications in optoelectronics and others. In particular, tuning the bandgap of such nanostructures can open up a new avenue for fabricating functional nano-devices. In the present article, we report the synthesis of 2D metallic Zn nanosheets at room temperature using a ball mill, which is capable of producing large-scale materials in a single run. Initially, nanoplates were formed for ball milling the octahedral-shaped Zn nanoparticles for the time of milling of 6 h. Subsequent ball milling for another 6 h leads these nanoplates to nearly uniform nanosheets. The thickness of these 2D nanostructures was found to decrease with an increase in the time of milling. Visible photoluminescence (PL) emissions centered at ∼3, ∼2.9, and ∼2.75 eV were observed from all the Zn particles showing semiconductor behavior. The origin of such semiconductor behavior was explained based on the radiative transition of electrons from the sp band to the upper states of the 3d band. This argument was confirmed through the studies of photoelectron spectroscopy and the first principle calculations employing density functional theory (DFT). Furthermore, excitation-dependent PL studies indicated that the bandgap of the 2D Zn nanostructures decreased with the increase in the ball milling time. Therefore, a redshift in the bandgap was observed with the increase in the ball milling time. Such changes in the bandgap with the thickness of 2D Zn nanostructures were also verified from the studies of DFT. Thus, the present study demonstrated that the bandgap of 2D metallic Zn nanostructures could be effectively tuned by reducing the thickness.