Plasma-deposited reactive species assisted synthesis of colloidal zinc-oxide nanostructures

Abstract

A surface-wave microwave discharge is applied to deposit reactive oxygen and nitrogen species (RONS) into the liquid subsequently used as a medium for laser ablation of a Zn metallic target. It is shown that during laser ablation in plasma-treated liquids the H2O2 concentration decreases, while in deionized water (DIW) significant H2O2 is produced. Meanwhile, the pH—initially adjusted by applying reductive metals—increases in the acidic liquids and decreases in the alkaline ones. During months of storage the pH of colloids stabilize around pH 6, which insures the long-term stability of RONS. It is demonstrated that in DIW metallic Zn NPs are created, which gradually oxidize during storage, while in the plasma-treated liquids ZnO NPs are produced with the mean size of 18 nm. In the alkaline plasma-treated liquid the NPs form large aggregates, which slows the dissolution of NPs. In the acidic and neutral solutions besides NPs nanosheets are also formed, which during storage evolve into nanosheet networks as a result of the dissolution of NPs. The band gap of the colloidal ZnO is found to decrease with the formation of aggregates and nanosheet networks. The ZnO NPs ablated in plasma-treated liquids exhibit a high-intensity visible emission covering the green-to-red spectral region. The photoluminescence spectra is dominated by the orange-red emission—previously not detected in the case of laser-ablated ZnO NPs and attributed to the interstitial Zn and oxygen sites—and the yellow emission, which can be attributed to the OH groups on the surface. It is shown that during months of storage, due to the dissolution of NPs and formation of nanosheets, the intensity of the visible emission decreases and shifts to the blue-green spectral region.