Hydrogen-related effects in the optical and surface electronic properties of ZnO
Thesis DisciplineElectrical Engineering
Degree GrantorUniversity of Canterbury
Degree NameDoctor of Philosophy (PhD)
This thesis concerns new hydrogen- and polarity-related effects in the photoluminescence of ZnO single crystal wafers and the relationship between surface electron accumulation and surface hydroxyl coverage on different ZnO surfaces. A comparative study of the low temperature photoluminescence of various types of hydrothermal and melt-grown ZnO wafers revealed several new hydrogen-related exciton recombination lines and a number of consistent polarity-related differences in the PL emission from different crystallographic surfaces. Temperature-dependent PL measurements were extensively used to distinguish the ground and excited state transitions involved in these effects. ZnO samples of different surface polarity were annealed in oxygen and nitrogen gases and in hydrogen-containing forming gas mixtures in an attempt to identify the origin of these new PL features. The well known aluminium-related I_₆ recombination line was resolved into two separate features in hydrothermal ZnO, and the new component I6-H (3.36081 eV) was found to repeatedly quench and then re-emerge after annealing in oxygen and forming gas, respectively. A model involving an aluminium - lithium - hydrogen defect complex was proposed for I6-H and further tested via hydrogen and deuterium implantation experiments on hydrothermal ZnO wafers with different lithium concentrations. These experiments also provided evidence for the involvement of a different lithium-hydrogen defect complex in other hydrogen-related emission lines I₄b,c (3.36219 eV and 3.36237 eV) unique to hydrothermal ZnO. In addition, a broad Gaussian-shaped feature observed in the near-band-edge PL emission from the O-polar (000‾1), a-plane (11‾20) and r-plane (1‾102) faces of ZnO was shown to be surface sensitive and also related to hydrogen. The involvement of hydrogen in the chemical and electronic properties of different ZnO surfaces was also investigated. The thermal stability of the hydroxyl termination and the associated downward surface band bending on the polar and non-polar surfaces of ZnO was studied by synchrotron and real-time photoelectron spectroscopy, both during and after annealing and subsequent H₂O/H₂ dosing in ultra-high vacuum conditions. On the O-polar face, the band bending could be reversibly switched over a range of approximately 0.8 eV by adjusting the surface H-coverage using simple UHV heat treatments and atmospheric exposure. A transition from electron accumulation to electron depletion on the O-polar face was observed at a H-coverage of approximately 0.9 monolayers. In contrast, the downward band bending on the Zn-polar face was signiﬁcantly more resilient and electron-depleted surfaces could not be prepared by heat treatment alone. This was also the case for in situ cleaving in UHV conditions which failed to produce hydroxyl-free surfaces due to migration of hydrogen from the bulk to the cleaved surface. Interestingly, the thermal stability of the hydroxyl termination on the a-plane (11‾20) and m-plane (10‾10) surfaces was signiifcantly lower than on the polar faces due to the availability of a lower energy desorption pathway and the electrostatic stability of these non-polar surfaces in their clean, bulk terminated form. The surface band bending on the non-polar ZnO surfaces was also found to be directly related to their OH coverage with a transition from downward to upward band bending, similar to that observed on the O-polar face, as the OH coverage was reduced. Thermal admittance spectroscopy and deep level transient spectroscopy was used to investigate the effect of lithium removal on the defect nature of hydrothermal ZnO. A number of new defects were introduced by the high temperature (1100-1400°C) annealing/re-polishing process used to reduce the lithium concentration, particularly E₁₉₀ (also known as T2) which is thought to be related to Zn vacancies. Significantly, both the E₅₀ defect level and the I6-H PL emission line were absent after lithium (and hydrogen) removal suggesting an association of both these features with the same aluminium - lithium - hydrogen defect complex.