Switch ‘on’ and ‘off’ ferromagnetic ordering through the induction and removal of oxygen vacancies and carriers in doped ZnO: A magnetization and electronic structure study

Abstract

The electronic structure and magnetic properties of cobalt‐doped (7.5%) and manganese co‐doped (2.5%) ZnO polycrystalline samples have been investigated to understand the mechanism of room temperature ferromagnetism (RTFM) in dilute magnetic semiconductors. The samples in powder form were annealed in argon and hydrogen atmospheres followed by their repressing into pellets and reheating in air. Rietveld analysis of X‐ray diffraction patterns confirmed the single‐phase nature of the samples in the wurtzite type hexagonal (P63mc) ZnO structure. The X‐ray photoelectron spectroscopy (XPS) results indicate that the Co and Mn atoms are in +2 oxidation states, which incorporate at the Zn2+ site, with no signature of metallic clusters. The Co‐doped sample prepared in air displays a paramagnetic state while the sample annealed in Ar atmosphere shows a weak ferromagnetic ordering at 300 K. The co‐doping of Mn further enhances the ferromagnetic ordering, indicating that Co and Mn ions play an additive role in inducing the ferromagnetic ordering in the ZnO matrix. Interestingly, the Co‐ and (Co + Mn)‐doped ZnO samples annealed in hydrogen atmosphere show a huge increment in the magnetic moment, however, the Mn ions seem to stay passive towards the hydrogen induced magnetization. Notably, the samples reheated in air show suppression of the induced ferromagnetism (FM). The resistance measurements suggest that the additional carriers induced upon hydrogenation also play some role in mediating the exchange coupling. The O 1s XPS and the XRD results show clear evidence of oxygen depletion in the samples upon hydrogenation, followed by a recovery upon their reheating in air. The observed FM is explained in terms of composite effect of the oxygen vacancies and the carrier density. Our results point out that the ferromagnetic ordering could be switched between ‘on’ and ‘off’ by introducing (through hydrogenation) and by removing (through reheating in air) the oxygen vacancies in Co‐doped ZnO.

Study of electronic and magnetic properties of vacuum annealed Cr doped ZnO

“…2b). These results demonstrate the evidence of an "on" and "off" switch action, identical to that reported in transition metal doped oxide systems of ZnO, TiO 2 , In 2 O 3 and CeO 2 [13,14,19,[23][24][25]. It is important to mention that the similar vacuum annealing of non-doped ZnO could not induce any RTFM in it.…”

“…These results establish that the magnetization and demagnetization process are reversible with regard to oxygen vacancies in agreement with Refs. [13,14,19,[23][24][25].…”

“…The ferromagnetism is observed in them [12][13][14][15], while the discrepancies continue in whether the ferromagnetism is intrinsic in nature [16][17][18][19] or due to spurious signals from the ferromagnetic impurities. By comparison, a lesser attention has been paid to Cr-and Ni-doped systems [20,21].…”

Enhancement of zinc vacancies in room-temperature ferromagnetic Cr–Mn codoped ZnO nanorods synthesized by hydrothermal method under high pulsed magnetic field

“…That is, the ZnO-Cr-Mn-4T sample has intrinsic ferromagnetism. Secondly, the relationship between the defects and the magnetism has been thought as an important factor of the RTFM [18]. According to the bound magnetic polarons (BMPs) model [48], …”

“…Singhal et al [18] reported that the codoping of Mn into Co doped ZnO further enhances the ferromagnetic ordering. Also, Aljawfi et al [19] suggested that the ferromagnetism of Cr/Co codoped ZnO nanoparticles improve with increasing Cr doping.…”