Unusual charge states and lattice sites of Fe in Al x Ga1−x N:Mn

Abstract Charge states and lattice sites of Fe ions in virgin and Mn-doped Al x Ga 1− x N samples were investigated using 57 Fe emission Mössbauer spectroscopy following radioactive 57 Mn + ion implantation at ISOLDE, CERN. In the undoped Al x Ga 1− x N, Fe 2+ on Al/Ga sites associated with nitrogen vacancies and Fe 3+ on substitutional Al/Ga sites are identified. With Mn doping, the contribution of Fe 3+ is considerably reduced and replaced instead by a corresponding emergence of a single-line-like component consistent with Fe 4+ on Al/Ga sites. Density functional theory calculations confirm the Fe 4+ charge state as stabilised by the presence of substitutional Mn 2+ in its vicinity. The completely filled spin up orbitals in Mn 2+ (3d 5 ) are expected to enhance magnetic exchange interactions. The population of the Fe 4+ state is less pronounced at high Al concentration in Al x Ga 1− x N:Mn, a behaviour attributable to hybridisation effects of 3d states to the semiconductor bands which weakens with increasing (decreasing) Al (Ga) content. Our results demonstrate that co-doping promotes the co-existence of unusual charge states of Fe 4+ and Mn 2+ , whereas their trivalent charge states prevail with either transition metal incorporated independently in III-nitrides. Co-doping thus opens up a new avenue for tailoring novel magnetic properties in doped semiconductors.