Free carrier-mediated ferromagnetism in nonmagnetic ion (Bi-Li) codoped ZnO nanowires

Non-magnetic dopants and p-type materials are attractive choices to explore the mechanism and origin of room-temperature defect-based ferromagnetism in metal oxide-based DMSs. In this study, we performed comprehensive transport, magnetic, structural, optical, and compositional as well as DFT studies of pristine, Li-doped, and Bi-Li codoped vertically aligned ZnO NW films to explore the mechanism and origin of ferromagnetism. We used a simple solution process to synthesize a wurtzite structure and vertically aligned ZnO NWs on a Si substrate. The doping, high crystallinity, and vertical alignment along the 002 planes were evidenced through HRTEM, FESEM, and XRD measurements. The XPS analysis confirmed the +1 and +3 states of Li and Bi, respectively. Moreover, Raman analysis also depicted the characteristic peaks of ZnO NWs at 98.31 cm^-1 and 437.71 cm^-1. The PL studies of doped NWs showed a typical NBE peak of ZnO at ∼395 nm along with a sub-gap defect-related broad peak at ∼504 nm indicating the presence of defects due to doping. The pure ZnO NW samples showed negligible saturation magnetization (M_s) at room temperature while the saturation magnetization was observed to increase with Li-doping and reduced with Bi-Li codoping. According to the Hall studies the pure ZnO NW film showed n-type conductivity, while all doped and codoped samples showed p-type conductivity. The hole concentration was observed to increase with Li-doping and decrease with Bi-Li codoping showing similar behavior to that of the M_s value, thereby suggesting a direct correlation between M_s and carrier concentration. The I-V properties showed a similar trend to that of carrier concentration and M_s. Our DFT studies showed that magnetization increased by Li doping and reduced by Li-Bi codoping in defective ZnO crystals by replacing Zn with Li and Bi atoms at the Zn site. Overall, our studies highlight the immense potential of hole-mediated Bi-Li codoped ZnO NW devices which are expected to play a pivotal role in developing spintronic devices.