Hydrogen-Assisted Molecular Beam Epitaxy of SiGeSn
Authors: Schwarz Daniel , Ziegler Johannes , Funk Hannes Simon , Schulze Joerg , Oehme Michael 
Published: November 2022

Since its first synthesis in 2003 [1], the ternary alloy semiconductor SiGeSn has seen an increasing interest due to its unique properties in the field of Group-IV semiconductors [2–6]. SiGeSn not only allows the decoupling of its bandgap and lattice-constant by what it is predestined for the epitaxy of strain-reduced heterostructures on the Si platform. Furthermore, SiGeSn becomes a direct bandgap semiconductor at high Sn concentrations. Considering these properties, SiGeSn is an attractive material system for optoelectronic applications. An exemplary heterojunction optoelectronic device is the single confinement heterostructure laser diode, the still missing key component for the monolithic integration of the optical on-chip communication on Si.
However, one of the greatest challenges faced by many Group-IV researchers is the epitaxy of SiGeSn bulk alloys with high crystal quality. The temperature induced segregation of Sn results in interstitial Sn atoms and subsequently in acceptor-like defect states, as it was already reported for GeSn [7].
In this work, we show the molecular beam epitaxy (MBE) of SiGeSn structures under Hydrogen ambient. First of all, we determined the concentration of the acceptor-like defect states of undoped SiGeSn NA,defect on the basis of capacitance-voltage (C-V) measurements of SiGeSn pin diodes. Furthermore, we investigated Hydrogen-assisted epitaxy as an approach for the reduction of the acceptor-like defect states.
All epitaxy experiments were performed in a 6” MBE system, where Si, Ge and Sn are used as matrix materials and B and Sb as dopants respectively. In particular, we investigated the influence of molecular (H2) as well as atomic (H) Hydrogen on the epitaxy process and therefore the quality of the grown structures. For this purpose, the MBE system was upgraded with a Hydrogen atom beam source for the generation of an atomic Hydrogen flux.
Since the Sn segregation is affected mostly by the substrate temperature, this critical growth parameter is measured in-situ using an infrared pyrometer, which allows the observation of the dynamic processes on the sample surface [8] and the precise control of the substrate temperature at TSub = 200 °C during the SiGeSn epitaxy.
All SiGeSn structures are based on Ge virtual substrates (Ge-VS) on Si(001) [9], followed by a 400 nm thick additional Ge buffer layer. In order to fulfil lattice matching of SiGeSn on Ge, a constant ratio of Si and Sn of Si/Sn = 3.67 was kept for all structures. The Sn concentration was varied in the range of 5 % < cSn < 10 %. For material characterization, 300 nm thick undoped SiGeSn layers were grown on this substrate layer stack (see Fig. 1a). A detailed characterization of the crystallinity and the surface roughness was performed using X-ray diffraction (XRD) and atomic force microscopy (AFM), respectively. The comparison of AFM micrographs of SiGeSn layers, grown with and without Hydrogen assistance (see Fig. 1b) show a clear reduction of the surface roughness due to Hydrogen assisted epitaxy.
In order to determine NA,defect, C-V measurements on SiGeSn pin diodes (see Fig. 1c) were performed. The diode layer structure, also based on the previously described substrate layer stack, starts with a 400 nm thick p-doped SiGeSn bottom layer with an acceptor concentration of NA = 5x1019 cm-3, followed by an 300 nm thick undoped SiGeSn layer and a closing 200 nm thick n-doped SiGeSn top layer with a donor concentration of ND = 5x1019 cm-3. Subsequently, pin diodes were fabricated using a single mesa process consisting of four basic steps: Mesa structuring using inductive coupled plasma reactive ion etching (ICP-RIE) with HBr, mesa passivation with plasma enhanced chemical vapor deposition (PECVD) grown SiO2, oxide window opening using RIE with CHF3 and metallization using sputtered Al. An exemplary device can be seen in the scanning electron microscopy (SEM) image in Fig. 1d.
The SiGeSn pin diodes were electrically characterised by means of C-V measurements using a Keithley 4200 semiconductor characterisation system. For further evaluation, the C-V characteristics of the pin diodes show linear behaviour when plotted on a C-2-V-scaled diagram (Fig. 1e). Under the assumption of a strongly asymmetric pn junction, (ND >> NA,defect), the slope m of the C-2-V characteristics is proportional to NA,defect. In this manner, we determined NA,defect for several SiGeSn pin diodes in dependence of the alloy composition. The results, as shown in Fig. 1f, show an acceptor-like defect concentration between 1017 cm-3 < NA,defect < 1018 cm-3, which is comparable with results reported by other groups for GeSn [7].
In our presentation, we will discuss Hydrogen-assisted epitaxy as a promising approach for improving the SiGeSn crystal quality.

Figure 1