Synthesis of Group IV Nanowires on Graphene: The Case of Ge Nanocrawlers.

In recent years, there has been a growing interest in using graphene as a synthesis platform for polymers, zero-dimensional (0D) materials, one-dimensional materials (1D), and two-dimensional (2D) materials. Here, we report the investigation of the growth of germanium nanowires (GeNWs) and germanium nanocrawlers (GeNCs) on single-layer graphene surfaces. GeNWs and GeNCs are synthesized on graphene films by gold nanoparticles catalyzed vapor-liquid-solid growth mechanism. The addition of hydrogen chloride gas (HCl) at the nucleation step increased the propensity toward GeNCs growth on the surface. As the time lag before HCl introduction during the nucleation step increased, a significant change in the number of out-of-plane GeNWs versus in-plane GeNCs was observed. The nucleation temperature and time played a key role in the formation of GeNCs as well. The fraction of GeNCs (χNCs) decreased from 0.95 ± 0.01 to 0.66 ± 0.07 when the temperature was kept at 305 °C for 15 s versus maintained at 305 °C throughout the process, respectively. GeNCs exhibit ⟨112⟩ as the preferred growth direction whereas GeNWs exhibit both ⟨112⟩ and ⟨111⟩ as the preferred growth directions. Finally, our growth model suggests a possible mechanism for the preference of an in-plane GeNC growth on graphene versus GeNW on SiO2. These findings open up unique opportunities for fundamental studies of crystal growth on graphene, as well as enable exploration of new electronic interfaces between group IV materials and graphene, potentially toward designing new geometries for hybrid materials sensors.