Silicon, arguably the most important technological semiconductor, is predicted to exhibit a range of new and interesting properties when grown in the hexagonal crystal structure. To obtain pure hexagonal silicon is a great challenge because it naturally crystallizes in the cubic structure. Here, we demonstrate the fabrication of pure and stable hexagonal silicon evidenced by structural characterization. In our approach, we transfer the hexagonal crystal structure from a template hexagonal gallium phosphide nanowire to an epitaxially grown silicon shell, such that hexagonal silicon is formed. The typical ABABAB... stacking of the hexagonal structure is shown by aberration-corrected imaging in transmission electron microscopy. In addition, X-ray diffraction measurements show the high crystalline purity of the material. We show that this material is stable up to 9 GPa pressure. With this development, we open the way for exploring its optical, electrical, superconducting, and mechanical properties.

Core–shell nanowires (NW) have become very prominent systems for band engineered NW heterostructures that effectively suppress detrimental surface states and improve performance of related devices. This concept is particularly attractive for material systems with high intrinsic surface state densities, such as the low-bandgap In-containing group-III arsenides, however selection of inappropriate, lattice-mismatched shell materials have frequently caused undesired strain accumulation, defect formation, and modifications of the electronic band structure. Here, we demonstrate the realization of closely lattice-matched radial InGaAs–InAlAs core–shell NWs tunable over large compositional ranges [x(Ga)∼y(Al) = 0.2–0.65] via completely catalyst-free selective-area molecular beam epitaxy. On the basis of high-resolution X-ray reciprocal space maps the strain in the NW core is found to be insignificant (ε < 0.1%), which is further reflected by the absence of strain-induced spectral shifts in luminescence spectra and nearly unmodified band structure. Remarkably, the lattice-matched InAlAs shell strongly enhances the optical efficiency by up to 2 orders of magnitude, where the efficiency enhancement scales directly with increasing band offset as both Ga- and Al-contents increase. Ultimately, we fabricated vertical InGaAs−InAlAs NW/Si photovoltaic cells and show that the enhanced internal quantum efficiency is directly translated to an energy conversion efficiency that is ∼3–4 times larger as compared to an unpassivated cell. These results highlight the promising performance of lattice-matched III–V core–shell NW heterostructures with significant impact on future development of related nanophotonic and electronic devices.