ZnAl2O4 decorated Al-doped ZnO tetrapodal 3D networks: microstructure, Raman and detailed temperature dependent photoluminescence analysis

Abstract

3D networks of Al-doped ZnO tetrapods decorated with ZnAl₂O₄ particles synthesised by the flame transport method were investigated in detail using optical techniques combined with morphological/structural characterisation. Low temperature photoluminescence (PL) measurements revealed spectra dominated by near band edge (NBE) recombination in the UV region, together with broad visible bands whose peak positions shift depending on the ZnO : Al mixing ratios. A close inspection of the NBE region evidences the effective doping of the ZnO structures with Al, as corroborated by the broadening and shift of its peak position towards the expected energy associated with the exciton bound to Al. Both temperature and excitation density-dependent PL results pointed to an overlap of multiple optical centres contributing to the broad visible band, with the peak position dependent on the Al content. While in the reference sample the wavelength of the green band remained unchanged with temperature, in the case of the composites, the deep level emission showed a blue shift with increasing temperature, likely due to distinct thermal quenching of the overlapping emitting centres. This assumption was further validated by the time-resolved PL data, which clearly exposed the presence of more than one optical centre in this spectral region. PL excitation analysis demonstrated that the luminescence features of the Al-doped ZnO/ZnAl₂O₄ composites revealed noticeable changes not only in deep level recombination, but also in the material's bandgap when compared with the ZnO reference sample. At room temperature, the ZnO reference sample exhibited free exciton resonance at ∼3.29 eV, whereas the peak position for the Al-doped ZnO/ZnAl₂O₄ samples occurred at ∼3.38 eV due to the Burstein–Moss shift, commonly observed in heavily doped semiconductors. Considering the energy shift observed and assuming a parabolic conduction band, a carrier concentration of ∼1.82 ×10¹⁹ cm⁻³ was estimated for the Al-doped ZnO/ZnAl₂O₄ samples.