Structural Insights on Microwave-Synthesized Antimony-Doped Germanium Nanocrystals

Doped and alloyed germanium nanocrystals (Ge NCs) are potential candidates for a variety of applications such as photovoltaics and near IR detectors. Recently, bismuth (Bi) as an n-type group 15 element was shown to be successfully and kinetically doped into Ge NCs through a microwave-assisted solution-based synthesis, although Bi is thermodynamically insoluble in bulk crystalline Ge. To expand the composition manipulation of Ge NCs, another more common n-type group 15 element for semiconductors, antimony (Sb), is investigated. Oleylamine (OAm)- and OAm/trioctylphosphine (TOP)-capped Sb-doped Ge NCs have been synthesized by the microwave-assisted solution reaction of GeI₂ with SbI₃. Passivating the Ge surface with a binary ligand system of OAm/TOP results in formation of consistently larger NCs compared to OAm alone. The TOP coordination on the Ge surface is confirmed by ³¹P NMR and SEM-EDS. The lattice parameter of Ge NCs increases with increasing Sb concentration (0.00-2.0 mol %), consistent with incorporation of Sb. An increase in the NC diameter with higher content of SbI₃ in the reaction is shown by TEM. XPS and EDS confirm the presence of Sb before and after removal of surface ligands with hydrazine and recapping the Ge NC surface with dodecanethiol (DDT). EXAFS analysis suggests that Sb resides within the NCs on highly distorted sites next to a Ge vacancy as well as on the crystallite surface. High Urbach energies obtained from photothermal deflection spectroscopy (PDS) of the films prepared from pristine Ge NC and Sb-doped Ge NCs indicate high levels of disorder, in agreement with EXAFS data. Electrical measurements on TiO₂-NC electron- and hole-only devices show an increase in hole conduction, suggesting that the Sb-vacancy defects are behaving as a p-type dopant in the Ge NCs, consistent with the vacancy model derived from the EXAFS results.