Atomistic Origins of Various Luminescent Centers and n-Type Conductivity in GaN: Exploring the Point Defects Induced by Cr, Mn, and O through an Ab Initio Thermodynamic Approach.

GaN is a technologically indispensable material for various optoelectronic properties, mainly due to the dopant-induced or native atomic-scale point defects that can create single photon emitters, a range of luminescence bands, and n- or p-type conductivities. Among the various dopants, chromium and manganese-induced defects have been of particular interest over the past few years, because some of them contribute to our present-day light-emitting diode (LED) and spintronic technologies. However, the nature of such atomistic centers in Cr and Mn-doped GaN is yet to be understood. A comprehensive defect thermodynamic analysis of Cr- and Mn-induced defects is essential for their engineering in GaN crystals because by mapping out the defect stabilities as a function of crystal growth parameters, we can maximize the concentration of the target point defects. We therefore investigate chromium and manganese-induced defects in GaN with ab initio methods using the highly accurate exchange-correlation hybrid functionals, and the phase transformations upon excess incorporation of these dopants using the CALPHAD method. We also investigate the impact of oxygen codoping that can be unintentionally incorporated during crystal growth. Our analysis sheds light on the atomistic cause of the unintentional n-type conductivity in GaN, being O N -related. In the case of Cr doping, the formation of Cr Ga defects is the most dominant, with an E +/0 charge transition at E VBM + 2.19 eV. Increasing nitrogen partial pressure tends to enhance the concentration of Cr Ga . However, in the case of doping with Mn, several different Mn-related centers can form depending on the growth conditions, with Mn Ga being the most dominant. Mn Ga possesses the E 2+/+ , E +/0 , and E 0/- charge transitions at 0.56, 1.04, and 2.10 eV above the VBM. The incorporation of oxygen tends to cause the formation of the Mn Ga -V Ga center, which explains a series of prior experimental observations in Mn-doped GaN. We provide a powerful tool for point defect engineering in wide band gap binary semiconductors that can be readily used to design optimal crystal growth protocols.