Shallow donors and acceptors in ZnO

In order to realize controlled p-type doping in ZnO the role of extrinsic and intrinsic donors has to be clarified. The extrinsic n-type dopants Al, Ga and In are commonly found in bulk ZnO crystals, but hydrogen also appears in relevant concentrations eventually controlling the residual n-type carrier concentrations in nominally undoped ZnO. The optical properties of excitonic recombinations in bulk, n-type ZnO are investigated by photoluminescence (PL). At liquid helium temperature the neutral donor-bound excitons dominate in the PL spectrum. Two electron satellite (TES) transitions of the donor-bound excitons allow us to determine the donor binding energies ranging from 46 to 73 meV. In the as-grown crystals a shallow donor with an activation energy of 30 meV controls the conductivity. Annealing annihilates this shallow donor which has a bound exciton recombination at 3.3628 eV. Correlated by magnetic resonance experiments we attribute this particular donor to hydrogen. These results are in line with the temperature-dependent Hall-effect measurements. The Al, Ga and In donor-bound exciton recombinations are identified based on doping and diffusion experiments, and using secondary ion mass spectroscopy. We report on the optical properties of the shallow nitrogen acceptor in ZnO incorporated by diffusion, by ion implantation and by in situ doping in epitaxial films.