Kinetics of Catalyst-Free and Position-Controlled Low-Pressure Chemical Vapor Deposition Growth of VO2 Nanowire Arrays on Nanoimprinted Si Substrates

In the present article, the position-controlled and catalytic-free synthesis of vanadium dioxide (VO2) nanowires (NWs) grown by the chemical vapor deposition (CVD) on nanoimprinted silicon substrates in the form of nanopillar arrays was analyzed. The NW growth on silicon nanopillars with different cross-sectional areas was studied, and it has been shown that the NWs' height decreases with an increase in their cross-sectional area. The X-ray diffraction technique, scanning electron microscopy, and X-ray photoelectron spectroscopy showed the high quality of the grown VO2 NWs. A qualitative description of the growth rate of vertical NWs based on the material balance equation is given. The dependence of the growth rate of vertical and horizontal NWs on the precursor concentration in the gas phase and on the growth time was investigated. It was found that the height of vertical VO2 NWs along the [100] direction exhibited a linear dependence on time and increased with an increase in the precursor concentration. For horizontal VO2 NWs, the height along the direction [011] varied little with the growth time and precursor concentration. These results suggest that the high-aspect ratio vertical VO2 NWs formed due to different growth modes of their crystal faces forming the top of the growing VO2 crystals and their lateral crystal faces related to the difference between the free energies of these crystal faces and implemented experimental conditions. The results obtained permit a better insight into the growth of high-aspect ratio VO2 NWs and into the formation of large VO2 NW arrays with a controlled composition and properties.