Bi-containing III-V semiconductors constitute an exciting class of metastable compounds with wide-ranging potential optoelectronic and electronic applications. However, the growth of III-V-Bi alloys requires group-III-rich growth conditions, which pose severe challenges for planar growth. In this work, we exploit the naturally-Ga-rich environment present inside the metallic droplet of a self-catalyzed GaAs nanowire to synthesize metastable GaAs/GaAs 1−x Bi x axial nanowire heterostructures with high Bi contents. The axial GaAs 1−x Bi x segments are realized with molecular beam epitaxy by first enriching only the vapor-liquid-solid (VLS) Ga droplets with Bi, followed by exposing the resulting Ga-Bi droplets to As 2 at temperatures ranging from 270 to 380 • C to precipitate arXiv:1903.11039v2 [cond-mat.mtrl-sci]

The self-assembly of heteroepitaxial GaN nanowires using either molecular beam epitaxy (MBE) or metal-organic vapor phase epitaxy (MOVPE) mostly results in wafer-scale ensembles with ultrahigh (>10 μm-2) or ultralow (<1 μm-2) densities, respectively. A simple means to tune the density of well-developed nanowire ensembles between these two extremes is generally lacking. Here, we examine the self-assembly of SiNx patches on TiN(111) substrates which are eventually acting as seeds for the growth of GaN nanowires. We first found that if prepared by reactive sputtering, the TiN surface is characterized by {100} facets for which the GaN incubation time is extremely long. Fast GaN nucleation is only obtained after deposition of a sub-monolayer of SiNx atoms prior to the GaN growth. By varying the amount of pre-deposited SiNx, the GaN nanowire density could be tuned by three orders of magnitude with excellent uniformity over the entire wafer, bridging the density regimes conventionally attainable by direct self-assembly with MBE or MOVPE. The analysis of the nanowire morphology agrees with a nucleation of the GaN nanowires on nanometric SiNx patches. The photoluminescence analysis of single freestanding GaN nanowires reveals a band edge luminescence dominated by excitonic transitions that are broad and blue shifted compared to bulk GaN, an effect that is related to the small nanowire diameter and to the presence of a thick native oxide. The approach developed here can be principally used for tuning the density of most III-V semiconductors nucleus grown on inert surfaces like 2D materials.

We introduce a facile route for the top-down fabrication of ordered arrays of GaN nanowires with aspect ratios exceeding 10 and diameters below 20 nm. Highly uniform thin GaN nanowires are first obtained by lithographic patterning a bilayer Ni/SiNx hard mask, followed by a combination of dry and wet etching in KOH. The SiNx is found to work as an etch stop during wet etching, which eases reproducibility. Arrays with nanowire diameters down to (33 ± 5) nm can be achieved with a uniformity suitable for photonic applications. Next, a scheme for digital etching is demonstrated to further reduce the nanowire diameter down to 5 nm. However, nanowire breaking or bundling is observed for diameters below ≈ 20 nm, an effect that is associated to capillary forces acting on the nanowires during sample drying in air. Explicit calculations of the nanowire buckling states under capillary forces indicate that nanowire breaking is favored by the incomplete wetting of water on the substrate surface during drying. The observation of intense nanowire photoluminescence at room-temperature indicates good compatibility of the fabrication route with optoelectronic applications. The process can be principally applied to any GaN/SiNx nanostructures and allows regrowth after removal of the SiNx mask.