General control of transition-metal-doped GaN nanowire growth: toward understanding the mechanism of dopant incorporation.

We report the first synthesis and characterization of cobalt- and chromium-doped GaN nanowires (NWs), and compare them to manganese-doped GaN NWs. Samples were synthesized by chemical vapor deposition method, using cobalt(II) chloride and chromium(III) chloride as dopant precursors. For all three impurity dopants hexagonal, triangular, and rectangular NWs were observed. The fraction of NWs having a particular morphology depends on the initial concentration of the dopant precursors. While all three dopant ions have the identical effect on GaN NW growth and faceting, Co and Cr are incorporated at much lower concentrations than Mn. These findings suggest that the doping mechanism involves binding of the transition-metal intermediates to specific NW facets, inhibiting their growth and causing a change in the NW morphology. We discuss the doping concentrations of Mn, Co, and Cr in terms of differences in their crystal-field stabilization energies (DeltaCFSE) in their gas-phase intermediates and in substitutionally doped GaN NWs. Using iron(III) chloride and cobalt(II) acetate as dopant precursors we show that the doping concentration dependence on DeltaCFSE allows for the prediction of achievable doping concentrations for different dopant ions in GaN NWs, and for a rational choice of a suitable dopant-ion precursor. This work further demonstrates a general and rational control of GaN NW growth using transition-metal impurities.