Control of nanocrystal topology and of the formation of selected polymorphs is an important feature for fundamental studies of crystal growth and for investigating the shape and structural dependence of many properties. 1 Such control is also critical in developing new pathways for materials synthesis 2 and new applications of nanostructured materials. 3 Conical nanostructures of carbon, 4a BN, 4b AlN, 4c SiC, 4d ZnO, 4e and Si 4f-g have attracted interest recently because of their potential uses in field emission, in nanoscaled manipulation, and as scanning probe microscopy and near-field scanning optical microscopy probes. Tapered nanostructures are expected to have higher bending stiffness than nanotubes and nanowires and better resistance to thermal-induced drift than nanowires. 5 Shape engineering of properties represents an important design flexibility for these and other applications. 6 Silicon-based nanostructures produced by bottom-up methods are highly attractive as key elements in emerging nanoelectronic device technologies due to performance superior to current topdown fabricated Si-based commercial devices and its cost-effectiveness for developing large-scaled electronic circuits. 7 Despite the number of polymorphs in bulk Si, nanostructured silicon materials produced by bottom-up methods have been limited to the diamondcubic (DC) structure. 8 Here, we report the metal-catalyzed chemical vapor deposition synthesis of Si and Ge solid nanocones (SiNCs, GeNCs) with control of apex angles. Significantly, we also find that the structure of the SiNCs is not the conventional DC phase, but rather diamond-hexagonal (DH).Evaporated and annealed 2 nm thick Au films or 2-30 nm diameter Au colloids (Ted Pella) cast on poly-L-lysine-functionalized SiO 2 -coated Si(100) substrates were exposed to flowing precursor of 10% SiH 4 in He, ∼20-200 sccm (10% GeH 4 in He, ∼50 sccm), and carrier gas of N 2 or 5% H 2 in Ar, ∼100 sccm (∼50 sccm) at 650°C (400°C) under ∼20 Torr (∼400 Torr) for synthesis of SiNCs (GeNCs) in a quartz tube furnace for 5-150 min. The resulting SiNCs and GeNCs were characterized by scanning electron microscopy (SEM, FEI-XL30), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM, JEOL 2010F), and Raman scattering spectroscopy (Renishaw 1000). TEM samples were prepared by sonicating the SiNCs and GeNCs from growth substrates in ethanol and dropping onto Ni or Cu TEM grids. Figure 1a shows an SEM image of a representative yield of SiNCs; the insets show a TEM image of a SiNC tip with a catalyst particle (upper) and an SEM of the hexagonal cross-section of a SiNC (lower). The SiNCs shown are ∼10 µm long, ∼2 µm wide at the base, and the typical tip radius r tip of the SiNC is ∼5 nm, though some possess catalyst-free tips with r tip ≈ 1-2 nm (not shown). Similar results were obtained with GeNCs (see Supporting Information). EDS analysis performed in TEM and SEM (not shown) confirms that each SiNC consists of Si throughout the structure. In addition, the SiNCs possess a re...