Heteroepitaxial Ge1-xMnx quantum dots (QDs) were grown on Si (001) by molecular beam epitaxial co-deposition, with x = 0 to 0.10, in order to explore the interaction between Mn content, surface morphological evolution, and magnetism. Morphological evolution typical of the Ge/Si (001) system was observed, where the effect of Mn on surface morphology is surprisingly minimal at low Mn content, with no obvious surface morphological indicators of second phase formation. As the Mn content increases, secondary phase formation becomes evident, appearing to heterogeneously nucleate on or within Ge QDs. Still higher Mn concentrations lead to extensive second phase formation interspersed with an array of Ge QDs. Although ferromagnetism up to 220 K is observed, likely arising from intermetallic precipitates, there is no clear evidence for room-temperature ferromagnetism associated with a dilute magnetic solution phase.

Heteroepitaxial Ge 0.98 Mn 0.02 quantum dots on Si (001) were grown by molecular beam epitaxy. The standard Ge wetting layer-hut-dome-superdome sequence was observed, with no indicators of second phase formation in the surface morphology. We show that Mn forms a dilute solid solution in the Ge quantum dot layer, and a significant fraction of the Mn partitions into a sparse array of buried, Mn-enriched silicide precipitates directly underneath a fraction of the Ge superdomes. The magnetic response from the ultra-thin film indicates the absence of robust room temperature ferromagnetism, perhaps due to anomalous intermixing of Si into the Ge quantum dots.

The interaction of Mn with Ge quantum dots (QD), which are bounded by {105} facets, and the strained Ge wetting layer (WL), terminated by a (001) surface, is investigated with scanning tunneling microscopy (STM). These surfaces constitute the growth surfaces in the growth of Mn-doped QDs. Mn is deposited on the Ge QD and WL surface in sub-monolayer concentrations, and subsequently annealed up to a temperature of 400 ° C. The changes in bonding and surface topography are measured with STM during the annealing process. Mn forms flat islands on the Ge{105} facet, whose shape and position are guided by the rebonded step reconstruction of the facet. Voltage-dependent STM images reflect the Mn-island interaction with the empty and filled states of the Ge{105} reconstruction. Scanning tunneling spectra (STS) of the Ge{105} facet and as-deposited Mn-islands show a bandgap of 0.8 eV, and the Mn-island spectra are characterized by an additional empty state at about 1.4 eV. A statistical analysis of Mn-island shape and position on the QD yields a slight preference for edge positions, whereas the QD strain field does not impact Mn-island position. However, the formation of ultra-small Mn-clusters dominates on the Ge(001) WL, which is in contrast to Mn interaction with unstrained Ge(001) surfaces. Annealing to T < 160 °C leaves the Mn-clusters on the WL unchanged, while the Mn-islands on the Ge{105} facet undergo first a ripening process, followed by a volume gain which can be attributed to the onset of intermixing with Ge. This development is supported by the statistical analysis of island volume, size and size distribution. Increasing the annealing temperature to 220° and finally 375 ° C leads to a rapid increase in the Mn-surface diffusion, as evidenced by the formation of larger, nanometer size clusters, which are identified as germanide Mn5Ge3 from a mass balance analysis. This reaction is accompanied by the disappearance of the original Mn-surface structures and de-wetting of Mn is complete. This study unravels the details of Mn-Ge interactions, and demonstrates the role of surface diffusion as a determinant in the growth of Mn-doped Ge materials. Surface doping of Ge-nanostructures at lower temperatures could provide a pathway to control magnetism in the Mn-Ge system.

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