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 (SiCl ₄ ) in a hot-wall chemical vapor deposition reactor. Even under the optimized conditions including H ₂ 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 H ₂ 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 SiCl ₄ /H ₂ 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.