We
performed a comprehensive investigation on the influence of
oxygen vacancies (VO) defects and their evolution under Mn substitution and
thermal annealing in different atmospheres on the ferromagnetic ordering
and optical energy band gap (E
g) of Mn-doped
ZnO thin films. All doped films showed a ferromagnetic phase at room
temperature, which became stronger at low temperatures. Our results
clearly showed a direct link between the concentration of VO and the observed ferromagnetism (FM). By increasing the Mn concentration
(C
Mn), both photoluminescence and X-ray
photoelectron spectroscopy results revealed an enhancement in the
concentration of VO, in parallel with a clear improvement
in the FM. In addition, the FM in the doped films became stronger
after annealing in vacuum and weaker after annealing in air, in accordance
with a considerable increase and decrease in the concentration of
VO that mediates the observed ferromagnetic order. The
results also indicated a direct correlation between the E
g behavior and the concentration of VO. Films
with a high C
Mn having a narrower E
g and higher VO level are found to
show stronger FM. On increasing the C
Mn, a slight shift in the E
g to lower values
is detected, indicating weak sp–d hybridization. All doped
films showed a single phase with würtzite structure, and the
Mn2+ ions are proved to substitute for the Zn2+ in the würtzite lattice.