Investigation of the influence of cadmium processing on zinc gallium oxide:manganese thin films for photoluminescent and thin film electroluminescent applications

Cadmium processing of ZnGa2O4 films provides a new fabrication route for phosphor powders and thin films. It relies on the enhanced diffusion due to the large vacancy concentration left by the sublimation of cadmium. Photoluminescent powders can be made with a single high temperature firing. Thin film devices can be processed at a significantly lower temperature, expanding the range of available substrates.; Powders and thin films of ZnGa2O4:Mn were fabricated using starting materials in which between 0% and 50% of the ZnO was substituted by CdO. It was found that the emission spectra of the various compositions was unaffected by the change in composition, peaking at 504 nm, with the colour coordinates x = 0.08 and y = 0.69. The invariance of the emission spectrum is due to the spinel crystal structure exhibited by the compound. However, the maximum PL brightness was obtained from powders in which 10% of the ZnO had been substituted by CdO in the starting materials. The improved brightness is the result of better manganese incorporation which resulted from CdO sublimation during processing. This left a large vacancy concentration which enhanced the diffusion, and hence the manganese incorporation. In the case of thin films sputtered from cadmium processed targets, the composition of the films as deposited closely mirrored that of the target starting materials. The as deposited films were not luminescent and had to be annealed in vacuum in order to activate the manganese. EDX of these films showed that all of the cadmium had sublimed during the anneal. Very long anneal times also resulted in the loss of zinc. The decomposition products were amorphous or nanocrystalline. These films had an identical PL emission to the powders. The loss of cadmium correlated with the onset of bright 254 nm photoluminescence in the films, indicating that cadmium loss aided in the activation of the manganese. This was the result of the enhanced diffusion due to the large vacancy concentration left by the sublimed material, which aided the incorporation and activation of the manganese. The cadmium in the sputtering targets also impacted the crystal structure of the films. Films from cadmium free targets exhibited a strong (111) x-ray diffraction peak, while those from cadmium processed targets more closely resembled the powder structure. The optimum thin film electroluminescent performance was obtained for films sputtered from targets processed with between 5% and 15% cadmium substituted for zinc. This was the result of improved diffusion during the anneals, due to the sublimation of cadmium oxide and the resulting large vacancy concentration. The best performance was obtained for films annealed at between 875°C and 900°C for 6--12 hours. These films exhibited both the maximum luminance (55 cd/m2 at 60 Hz) and the lowest transferred charge (∼20 muC/cm2). This combined for a peak efficiency of 0.5 lm/W at 60 Hz). Beyond 12 hours at 900°C or temperatures higher than this, EL performance degraded due to the decomposition of the thin film. It was concluded that the luminescent performance of this material is strongly influenced by the loss of cadmium during processing. The enhanced diffusion afforded by the cadmium sublimation results in improved EL performance at annealing temperature lower that that of pure zinc gallate.