Optical and electronic properties of native zinc oxide films on polycrystalline Zn

The oxide layer spontaneously formed on zinc and an "electrochemically reduced" oxide has been characterised by a combination of X-ray photoelectron spectroscopy (XPS) and spectroscopic ellipsometry (SE). The onset of the main electronic absorption, which is directly related to the bandgap, is extracted from the SE measurements. The SE results are compared with simulations on the basis of zinc and bulk zinc oxide optical constant data. Measurements in the ultraviolet and visible (UV-vis) spectral range show the presence of an absorption at ∼1.8 eV (680 nm) which is unaccounted for from the bulk data, and is likely to originate from intragap energy levels, implicating the presence of surface defects in the layers. Analysis of the Zn LMM Auger peaks in XPS data show the presence of Zn different from bulk zinc and bulk ZnO, attributed to excess Zn in the oxide films. Mid-infrared (IR) ellipsometry shows two peaks around 0.12 and 0.15 eV (1000 and 1200 cm(-1)), which strengthen the assumption of the presence of a locally distorted structure in the oxide layers. Electrochemically reduced samples show a much thinner oxide layer and higher Zn-doping concentration films than samples purely dipped in NaOH solution. Using a self-contained multiple sample SE analysis, estimates of the refractive index and absorption coefficient (i.e., the optical constants) of the oxide films are presented from 1.5-4.4 eV (280 to 810 nm).