By employing various high-resolution metrology techniques we directly probe the material composition profile within GaAs-Al0.3Ga0.7As core-shell nanowires grown by molecular beam epitaxy on silicon. Micro Raman measurements performed along the entire (>10 μm) length of the [111]-oriented nanowires reveal excellent average compositional homogeneity of the nominally Al0.3Ga0.7As shell. In strong contrast, along the radial direction cross-sectional scanning transmission electron microscopy and associated chemical analysis reveal rich structure in the AlGaAs alloy composition due to interface segregation, nanofaceting, and local alloy fluctuations. Most strikingly, we observe a 6-fold Al-rich substructure along the corners of the hexagonal AlGaAs shell where the Al-content is up to x ~ 0.6, a factor of 2 larger than the body of the AlGaAs shell. This is associated with facet-dependent capillarity diffusion due to the nonplanarity of shell growth. A modulation of the Al-content is also found along the radial [110] growth directions of the AlGaAs shell. Besides the ~10(3)-fold enhancement of the photoluminescence yield due to inhibition of nonradiative surface recombination, the AlGaAs shell gives rise to a broadened band of sharp-line luminescence features extending ~150-30 meV below the band gap of Al0.3Ga0.7As. These features are attributed to deep level defects under influence of the observed local alloy fluctuations in the shell.

We investigated the interwire distance dependence on the growth kinetics of vertical, high-yield InAs nanowire arrays on Si(111) grown by catalyst-free selective area molecular beam epitaxy (MBE). Utilizing lithographically defined SiO2 nanomasks on Si(111) with regular hole patterns, catalyst-free and site-selective growth of vertically (111)-oriented InAs nanowires was achieved with very high yields of ∼90 percent. Interestingly, the yield of vertically ordered nanowires was independent of the interwire distance and the initial growth stages. Significant size variation in the nanowires was found to depend critically on the interwire distance and growth time. Two growth regimes were identified—(i) a competitive growth regime with shorter and thinner nanowires for narrow interwire distances and (ii) a diffusion-limited growth regime for wider distances, providing good estimates for the surface diffusion lengths. Surprisingly, despite these size-dependent effects the nanowire geometries remained unaltered with uniform, almost nontapered morphologies even over large variation in nanowire density (∼mid−106–109 cm−2 range). X-ray diffraction further confirmed the vertical (111) directionality with low crystal tilt by rocking curve widths (ω scans) as low as ∼0.6°. These findings demonstrate the capability to precisely tailor the position and size of well-oriented III-V semiconductor nanowires through noncatalytic MBE selective area growth and provide an important step toward fully integrated, uniform vertical III-V nanowire array-on-Si devices.

We identify a new noncatalytic growth regime for molecular beam epitaxially grown GaAs nanowires (NWs) that may provide a route toward axial heterostructures with discrete material boundaries and atomically sharp doping profiles. Upon increase of the As/Ga flux ratio, the growth mode of self-induced GaAs NWs on SiO(2)-masked Si(111) is found to exhibit a surprising discontinuous transition in morphology and aspect ratio. For effective As/Ga ratios <1, in situ reflection high-energy electron diffraction measurements reveal clear NW growth delay due to formation of liquid Ga droplets since the growth proceeds via the vapor-liquid-solid mechanism. In contrast, for effective As/Ga ratios >1 an immediate onset of NW growth is observed indicating a transition to droplet-free, facet-driven selective area growth with low vertical growth rates. Distinctly different microstructures, facet formation and either the presence or absence of Ga droplets at the apex of NWs, are further elucidated by transmission electron microscopy. The results show that the growth mode transition is caused by an abrupt change from As- to Ga-limited conditions at the (111)-oriented NW growth front, allowing precise tuning of the dominant growth mode.