Growth of Metal-Nitride Thin Films by Pulsed Laser Deposition
Degree GrantorUniversity of Canterbury
Degree NameDoctor of Philosophy
The growth of thin-film metal nitride materials from elemental metal targets by plasma-assisted pulsed laser deposition (PLD) has been explored and analysed. A new UHV PLD growth system has been installed and assembled and its system elements were calibrated. A series of GaN thin films have been grown to calibrate the system. In-situ RHEED indicated that the films were single crystal and that growth proceeded in a three-dimensional fashion. SEM images showed heavy particulation of film surfaces that was not in evidence for later refractory metal nitride films. This may be connected to the fact that Ga targets were liquid while refractory metals were solid. Most GaN films were not continuous due to insufficient laser fluence. Continuous films did not exhibit photoluminescence. HfN films have been grown by PLD for the first time. Films grown have been shown to have high reflectivity in the visible region and low resistivity. These factors, along with their crystal structure, make them suitable candidates to be used as back-contacts in GaN LEDs and could also serve as buffer layers to enable the integration of GaN and Si technologies. Growth factors affecting the films’ final properties have been investigated. Nitrogen pressure, within the operating range of the plasma source, has been shown to have little effect on HfN films. Substrate temperature has been demonstrated to have more influence on the films’ properties, with 500 °C being established as optimum. ZrN films have also been grown by PLD. Early results indicated that they exhibit reflectivities 50 % ± 5 % lower than those of HfN. However, further growth and characterisation would be required in order to establish this as a fundamental property of ZrN as nitride targets were mostly used in ZrN production. Single-crystal epitaxial GdN and SmN films have been produced by PLD. This represents an improvement in the existing quality of GdN films reported in the literature, which are mostly polycrystalline. In the case of SmN, these are the first epitaxial films of this material to be grown. Film quality has been monitored in-situ by RHEED which has allowed growth to be tailored to produce ever-higher crystal quality. Post-growth analyses by collaborators was also of assistance in improving film growth. Substrate temperatures and nitrogen plasma parameters have been adjusted to find optimum values for each. In addition, laser fluence has been altered to minimise the presence of metal particulates in the films, which interfere with magnetic measurements carried out in analyses. Capping layers of Cr, YSZ or AlN have been deposited on the GdN and SmN prior to removal from vacuum to prevent their degradation upon exposure to atmospheric water vapour. The caps have been steadily improved over the course of this work, extending the lifetime of the nitride films in ambient. However, they remain volatile and this may persist since water vapour can enter the film at the edge regardless of capping quality. Optical transmission has shown an onset of absorption at 1.3 eV for GdN and 1.0 eV for SmN.