Cation and anion doping of ZnO thin films by spray pyrolysis

Thesis

ZnO is an n-type semiconducting material with high optical transparency in the visible range (400 - 750 nm) of the electromagnetic spectrum. When doped with group 13 or 14 metal oxides, ZnO exhibits almost metallic electrical conductivity. ZnO thin films have been recognised as promising alternative material for the currently widely-used but expensive indium oxide in the form of indium tin oxide (ITO), in terms of their low cost and the high abundance of zinc. At the moment, even the best solution-processed ZnO films still can not compete for ITO replacement especially in solar energy utilization and OLED lighting applications, and the performance of ZnO films needs to be further improved. The objective of this work was to enhance the electrical and optical properties of spray pyrolysed ZnO thin films by simultaneous cation and anion doping. This was achieved by growing several series of undoped, single-doped, and co-doped ZnO thin films over a wide range of conditions, in order to understand the growth behaviour of undoped and doped ZnO, and to establish the optimum growth procedure. Spray pyrolysis process has advantages over vacuum-based techniques in terms of its low-cost, high deposition rate, simple procedure and can be applied for the production of large area thin films. Various techniques were employed to characterize the properties of the prepared thin films, and thus determine the optimum growth conditions (i.e. X-ray difiraction (XRD), Xray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), scanning electron microscopy (SEM), UV-Vis-NIR spectroscopy and Hall effect measurement).

The growth of doped ZnO on glass substrates using Si and F as dopants, yielded highly conducting and transparent thin films. The co-doped thin films exhibited distinct widening of band gap upon increasing deposition temperature and doping concentration as a result of increasing electron concentration up to 4.8 x 10²⁰ cm^-3 upon doping with Si and F at the same time. The resistivity of the films deposited from Zn(acac)₂ · xH₂O solutions and at the optimum temperature of 450 °C, was found to decrease from 4.6 x 10^-2 Ωcm for the best undoped ZnO film to 3.7 x 10^-3 Ωcm, upon doping with 3% Si. The films co-doped with Si and F in the ratios of [Si] / [Zn]= 3 - 4 mol% and [F] / [Zn]=30 - 40 mol% were the most conducting (p ∼ 2.0 x 10^-3 Ωcm). The associated optical transmittance of co-doped ZnO was above 85% in the whole visible range. Results compare favourably with In-doped ZnO deposited under similar conditions. Si+F co-doped ZnO films offer a suitable replacement for ITO in many applications such as LCD and touch screen displays.

Authors: Rashidi-Alavijeh, N

• Type of award: DPhil
• Level of award: Doctoral
• Awarding institution: University of Oxford