The growth of Sn-rich group-IV semiconductors at the nanoscale can enrich the understanding of the fundamental properties of metastable GeSn alloys. Here, we demonstrate the effect of the growth conditions on the morphology and composition of Ge/GeSn core/shell nanowires by correlating the experimental observations with a theoretical interpretation based on a multiscale approach. We show that the cross-sectional morphology of Ge/GeSn core/shell nanowires changes from hexagonal to dodecagonal upon increasing the supply of the Sn precursor. This transformation strongly influences the Sn distribution as a higher Sn content is measured under the {112} growth front. Ab initio DFT calculations provide an atomic-scale explanation by showing that Sn incorporation is favored at the {112} surfaces, where the Ge bonds are tensile-strained. A phase-field continuum model was developed to reproduce the morphological transformation and the Sn distribution within the wire, shedding light on the complex growth mechanism and unveiling the relation between segregation and faceting. The tunability of the photoluminescence emission with the change in composition and morphology of the GeSn shell highlights the potential of the core/shell nanowire system for optoelectronic devices operating at mid-infrared wavelengths.

Strain engineering in Sn-rich group IV semiconductors is a key enabling factor to exploit the direct bandgap at mid-infrared wavelengths. Here, we investigate the effect of strain on the growth of GeSn alloys in a Ge/GeSn core/shell nanowire geometry by controlling the Ge core diameter and correlating the results with theoretical strain calculations. Incorporation of the Sn content in the 10-20 at. % range is achieved with Ge core diameters ranging from 50 nm to 100 nm. While the smaller cores lead to the formation of a regular and homogeneous GeSn shell, larger cores lead to the formation of multifaceted sidewalls and broadened segregation domains, inducing the nucleation of defects. This behavior is rationalized in terms of the different residual strain, as obtained by realistic finite element method simulations. The extended analysis of the strain relaxation as a function of core and shell sizes, in comparison with the conventional planar geometry, provides a deeper understanding of the role of strain in the epitaxy of metastable GeSn semiconductors.

We address the role of non-uniform composition, as measured by energy-dispersive x-ray spectroscopy, in the elastic properties of core/shell nanowires for the Ge/GeSn system. In particular, by finite element method simulations and transmission electron diffraction measurements, we estimate the residual misfit strain when a radial gradient in Sn and a Ge segregation at the nanowire facet edges are present. An elastic stiffening of the structure with respect to the uniform one is concluded, particularly for the axial strain component. More importantly, refined predictions linking the strain and the Sn percentage at the nanowire facets enable us to quantitatively determine the maximum compressive strain value allowing for additional Sn incorporation into a GeSn alloy. The progressive incorporation with increasing shell thickness, under constant growth conditions, is specifically induced by the nanowire configuration, where a larger elastic relaxation of the misfit strain takes place.