Material properties of ZnO thin films prepared by spray pyrolysis

Ph.D.In the search to improve the conversion efficiency of solar cells such as α-Si and CuInSe2 cells, attention have recently been focused on the use of transparent conducting oxides (TCO's) as window layers and top electrodes in these cells. Materials such as indium tin oxide (ITO) and fluorine-doped tin oxide (FTO) thin films were used due to their excellent electro-optical properties, but it was found that they were unstable when subjected to a hydrogen plasma (during the a-Si deposition) and that the materials reduced to their metallic forms, degrading their electrical and optical properties. Zinc oxide (ZnO), however, possess electrical and optical properties equal to ITO and FTO, but is stable in the presence of a hydrogen plasma. In this study a system for the deposition of ZnO thin films by spray pyrolysis was developed and the films successfully deposited. The films were also doped with A1C1 3 in an attempt to further improve the films' conductivities. The films were then characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), electrical measurements (Hall and four-point probe measurements) and optical analyses of the films. The films were compared with films deposited by atomic layer epitaxy (ALE) and DC sputtering. It was found that the films were crystalline with a predominantly (002) preferred orientation. The addition of Al as dopant, however, resulted in the film structure deteriorating. The SEM micrographs obtained of the films indicated films with a close-packed structure, existing of small grains and the film surface having a textured appearance. It was further found that the deposition parameters of the films influenced both the structures of the films and the morphologies and the micrographs indicated that the addition of Al as dopant resulted in the film formation being inhibited and even resulting in no proper film being deposited. It was found that the as-deposited ZnO films were resistive and that the films had to be subjected to a post-deposition annealing to decrease the film resistivity. The annealing conditions were investigated and it was found that annealing the films in hydrogen at their deposition temperature for an hour resulted in the largest decrease in the films' resistivities, typically two orders of magnitude. Studies of the substrate temperature indicated that the films had to be deposited at between 350 and 420°C and that a reduction in the substrate temperature resulted in the film resistivity increasing. Contrary to literature, it was found that the addition of Al as dopant had no beneficial influence on the electrical properties of the films and that dopant concentrations exceeding 1.0 at.% resulted in the film resistivity increasing. The films were characterized optically by analysing the transmission spectra obtained of the films, using the envelope technique. It was found that the films had transmissions exceeding 95% and that the refractive indices and optical gaps centred around 1.99 and 3.3 eV respectively. Both properties were affected by the deposition parameters. The ZnO films deposited by spray pyrolysis compared excellently with the films prepared by ALE and DC sputtering in all aspects. It is hence clear that ZnO films, with characteristics suitable for solar cell application, can be deposited by the simple and inexpensive technique of spray pyrolysis