Interactions between gallium and nitrogen dopants in ZnO films grown by radical-source molecular-beam epitaxy

It has been recently predicted that the co-doping of an acceptor (nitrogen) and a donor (aluminum, gallium, indium) in a 2:1 ratio will dope ZnO p-type due to a reduction in the Madelung energy making the nitrogen acceptor energy level more shallow. We have been growing gallium and nitrogen co-doped ZnO films by radical-source molecular-beam epitaxy by use of oxygen and nitrogen radicals supplied via rf radical source cells. Diode-like current–voltage characteristics and donor acceptor pair-like photoluminescence emission were observed for a Ga and N doped ZnO film grown on an undoped ZnO buffer layer. However, Hall measurements revealed that the conductivity was n-type. Formation of a non-ZnO phase in the sample was confirmed by secondary ion mass spectroscopy and x-ray diffraction measurements. Zn and $\mathrm{Zn+O}$ secondary ion intensities fell sharply by two orders of magnitude in going from the undoped ZnO layer to the highly co-doped ZnO. X-ray diffraction measurements indicated the formation of ${\mathrm{ZnGa}}_{\mathrm{2}}{\mathrm{O}}_{\mathrm{4}}.$