A reliable method to grow vertically-aligned silicon nanowires by a novel ramp-cooling process

We have grown silicon nanowires (SiNWs) on Si (1 1 1) substrates by gold-catalyzed vapor–liquid–solid (VLS) process using tetrachlorosilane (SiCl4) in a hot-wall chemical vapor deposition reactor. Even under the optimized conditions including H2 annealing to reduce the surface native oxide, epitaxial SiNWs of 150–200 nm in diameter often grew along all four 〈1 1 1〉 family directions with one direction vertical and three others inclined to the surface. Therefore, the growth of high degree ordered SiNW arrays along [1 1 1] only was attempted on Au-coated Si (1 1 1) by a ramp-cooling process utilizing the liquid phase epitaxy (LPE) mechanism. The Au-coated Si substrate was first annealed in H2 at 650 °C to form Au–Si alloy nanoparticles, and then ramp-cooled at a controlled rate to precipitate epitaxial Si seeds on the substrate based on LPE mechanism. The substrate was further heated in SiCl4/H2 to 850 °C for the VLS growths of SiNWs on the Si seeds. Thus, almost 100% vertically-aligned SiNWs along [1 1 1] only could be reproducibly grown on Si (1 1 1), without using a template or patterning the metal catalyst. The high-density vertically-aligned SiNWs have good potentials for solar cells and nano-devices.