Effects of Laser Ablation on Growth of ZnO/ZnS/ZnO Multilayer Structured Nanorods by Chemical Vapor Deposition

Abstract

ABSTRACTZnO is an attractive II-VI compound semiconductor material for various optoelectronic devices. Recently, growth of various nanostructures of ZnO such as nanorod, nanobelt, nanowall, etc. has been reported, and ZnO has been considered as a promising material for nanodevices. We have studied on fabrication of aligned ZnO nanorods by a low-pressure thermal chemical vapor deposition (CVD) method cooperated with laser ablation of Mn pellet. In this paper, we report on fabrication of ZnO/ZnS/ZnO multilayer structured nanorods and particularly on effects of laser ablation on the morphology of the nanorods intending to develop a new electroluminescent device including ZnO nanorods. The fabrication method of ZnO/ZnS/ZnO multilayer structured nanorods is almost same method used in our previous study. Metal Zn vapor and O2 gas or H2S are used as precursors to synthesize ZnO or ZnS, and N2 is used as carrier gas. A Mn pellet is placed near a Si(111) substrate in a deposition chamber and ablated by a pulsed Nd:YAG laser beam (wavelength =1.064 mm, pulse width = 8 ns, repetition frequency = 10 shots/sec). The pressure is 13.3 Pa and the temperature is 550 C. When ZnO is grown, O2 of 0.88 SCCM mass flow rate is used as a precursor. When ZnS is grown, on the other hand, H2S of 2.0 SCCM mass flow rate is used as a precursor. The growth time is 15 min for each layer. Firstly, ZnO nanorods are grown. Laser ablation of Mn is executed for initial 3 min and only CVD is performed for remaining 12 min. The vertically aligned ZnO nanorods with 100 nm diameter and 1500 nm height are grown. Secondly, ZnS nanorod is grown on the top surface of the first ZnO nanorods. In this process, the morphology is not so dependent on execution of laser ablation of Mn for initial 3 min in this growth process. Finally, ZnO layer is again grown on ZnS/ZnO nanorods described above. When the laser ablation of Mn for initial 3 min is not executed, many fine ZnO whiskers with long length are grown with random directions on the top surface and on the side surfaces of ZnS/ZnO nanorods. When the laser ablation of Mn for initial 3 min is executed, on the other side, a thick whisker is grown on top surface of ZnS/ZnO nanorods. The shape is not nanorod. The diameter is abruptly decreased and the tip is very sharp. The growth of ZnO whisker on the side surface of ZnS/ZnO nanorods is not almost observed. It is found that the laser ablation of Mn for initial 3 min in the third ZnO growth strongly influences the morphology of the third ZnO layer. We estimate that the Mn species that are ablated from a Mn pellet and reaches the surface of ZnS/ZnO nanorods change any quality of the surface of ZnS/ZnO nanorods. We are now studying of finding the growth conditions of the third ZnO layer with morphology of nanorod on ZnS/ZnO nanorods that is considered to be suitable for electroluminescent devices.