Effects of Substrate and Post-Growth Treatments on the Microstructure and Properties of ZnO Thin Films Prepared by Atomic Layer Deposition

Aluminum doped zinc oxide (ZnO:Al) thin films were synthesized by atomic layer deposition on silicon, quartz and sapphire substrates and characterized by X-ray diffraction (XRD), high-resolution scanning electron microscopy (SEM), optical spectroscopy, conductivity mapping, Hall-effect measurements and positron annihilation spectroscopy (PAS). XRD showed that the as-grown films are of single-phase ZnO wurtzite structure and do not contain any secondary or impurity phases. The type of substrate was found to affect the orientation and degree of crystallinity of the films but had no effect on the defect structure or the transport properties of the films. High conductivity of 10-3 Ohm cm, electron mobility of 20 cm2/Vs and carrier density of 1020 cm-3 were measured in most films. Thermal treatments in various atmospheres induced a large effect on the thickness, structure and electrical properties of the films. Annealing in a Zn and nitrogen environment at 400 oC for one hour led to a 16% increase in the thickness of the film; this indicates that Zn extracts oxygen atoms from the matrix and forms new layers of ZnO. On the other hand, annealing in a hydrogen atmosphere led to the emergence of an Al2O3 peak in the XRD pattern, which implies that hydrogen and Al atoms compete to occupy Zn sites in the ZnO lattice. Only ambient-air anneal had an effect on film defect density and electrical properties, generating reduction in conductivity and electron mobility. Depth resolved measurements of positron annihilation revealed short positron diffusion lengths and high concentration of defects in all as-grown films. However these defects did not diminish the electrical conductivity in the films.