Fabrication and Characterisation of Zinc Oxide Thin Films Singly doped With Trace amounts of Rare Earth Materials
Degree GrantorUniversity of Canterbury
Degree NameDoctor of Philosophy
Two sets of nanostructured Zinc Oxide (ZnO) thin films doped with varying nominal concentrations of rare earth (RE) ions were prepared by pulsed laser deposition (PLD). One set was doped with europium ions (ZnO:Eu³⁺) while the other was doped with erbium ions (ZnO:Er³⁺). The nominal concentration of RE ions ranged from 0.025 to 5 atomic %. The produced films were structurally, morphologically and optically characterised using different techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL), combined excitation and emission spectroscopy (CEES) and X-ray photoelectron spectroscopy (XPS).
All films were found to possess a single-crystal hexagonal structure and were strongly oriented along the c-axis. However, the crystallinity of the investigated films seemed to deteriorate as the concentration of the rare earth ions increased. This deterioration is assumed to be due to the local distortion of the ZnO structure (host material) caused by the insertion of the relatively large RE ions, hence inducing structural stresses.
Importantly, XRD measurements showed that no other crystalline phases related to europium or erbium, such as Eu₂O₃ or Er₂O₃, were observed. Surprisingly, the ZnO lattice constant (c) tended to become smaller as more RE³⁺ ions were added to the films. An explanation is offered whereby this observation can be taken as further evidence that Zn²⁺ ions were successfully substituted by RE³⁺ ions. Interestingly, doping ZnO films with RE³⁺ ions of a nominal concentration of ≥ 0.5 at.% or higher exhibited a drastic effect on the optical properties of the host matrix (ZnO) in which the near band edge luminescence characteristic of pure ZnO completely disappeared.
According to SEM images, morphological changes also occur as dopant concentrations increase. Well-defined grains (crystallites) were clearly seen in films doped with ˂ 0.5 at.% of RE ions. However, these grains became hardly distinguishable at higher RE ion concentrations.
Typical intra-4f shell transitions of RE³⁺ ions were observed when these ions were non-resonantly excited with UV radiation, indicating that energy had been efficiently transferred from ZnO to the rare earth ions. A plausible physical mechanism for this energy transfer is proposed.
The radiative optical centres of rare earth ions were studied by CEES. In these experiments, both sets of films exhibited multiple optical sites. ZnO:Eu³⁺ thin films were found to have two distinct optical sites with differing site symmetries, whereas up to four optical sites were detected in the ZnO:Er³⁺ films.