Post-Deposition Induced Conductivity in Pulsed Laser Irradiated Metal Doped Zinc Oxide Films
The optical and electrical properties of doped solution-deposited and rf sputter-deposited thin metal oxide films were investigated following post deposition pulsed laser irradiation. Solution deposited films were annealed at 450 ºC. Following the heating regiment, the transparent metal oxide films were subjected to 355 nm pulsed Nd:YAG laser irradiation (4 nsec pulsewidth) at fluences between 5 and 150 mJ/cm2. Irradiation times at pulse frequencies of 30 Hz ranged from seconds to tens of minutes. Film densification, index change and a marked increase in conductivity were observed following irradiation in air and under vacuum of Al:ZnO (AZO), Ga:ZnO (GZO), and In:ZnO (IZO) films deposited on silica substrates. Despite the measured increase in conductivity, all films continued to show high transparency on the order of 90% at wavelengths from the band edge well into the near infrared region of the spectrum. Laser energies required for turning on the conductivity of these films varied depending upon the dopant. Irradiations in air yielded resistivity measurements on the order of 16 Ωcm. Resistivities of films irradiated under vacuum were on the order of 0.1 Ωcm. The increase in conductivity can be attributed to the formation of oxygen vacancies and subsequent promotion of free carriers into the conduction band. All irradiated films became insulating again after around 24 hours. Oxygen atoms in air became reduced by electrons in the metal conduction band and diffused into vacancies in the lattice. The rate of this reduction process depends on the type of dopant. This work also sheds light on the damage threshold, correlating the optical properties with the presence of free carriers that have been introduced into the conduction band. All films were characterized by means of UV-VIS-NIR transmission spectroscopy, visible and UV Raman spectroscopy and Hall measurements. Analysis of interference fringes in measured transmission spectra allowed film density and refractive index to be evaluated while the Raman measurements showed an increase in LO mode intensity with respect to the TO mode intensity as the films became more conducting. Results of this study are not only important for the continued development of transparent conducting oxide films that find use in photovoltaic cells and solid state lighting modules, but also provide evidence for the role of free carriers in initiating the laser damage process in these wide bandgap metal oxide films.The Journal of Young Investigators is not affiliated with the US Department of Energy. This paper was written by a student intern with the Department of Energy and does not constitute a declarative position of either the Department of Energy or the Journal of Young Investigators.