Residual and intentional n-type doping of ZnO thin films grown by metal-organic vapor phase epitaxy on sapphire and ZnO substrates

Abstract

ZnO epilayers usually exhibit high n-type residual doping which is one of the reasons behind the difficulties to dope this material p-type. In this work, we aimed at determining the nature of the involved impurities and their potential role as dopant in ZnO thin films grown by metalorganic vapor phase epitaxy (MOVPE) on sapphire and ZnO substrates. In both cases, secondary ion mass spectroscopy (SIMS) measurements give evidence for a strong diffusion of impurities from the substrate to the epilayer, especially for silicon and aluminum. In the case of samples grown on sapphire substrates, aluminum follows Fick's diffusion law on a wide growth temperature range (800−1000°C). Thus, the saturation solubility and the diffusion coefficient of aluminum in ZnO single crystals have been determined. Furthermore, the comparison between SIMS impurity and effective dopant concentrations determined by capacitance-voltage measurements highlights, on one hand a substitutional mechanism for aluminum diffusion, and on the other hand that silicon acts as a donor in ZnO and not as an amphoteric impurity. In addition, photoluminescence spectra exhibit excitonic recombinations at the same energy for aluminum and silicon, indicating that silicon behaves as an hydrogenic donor in ZnO. Based on these experimental observations, ZnO thin films with a controlled n-type doping in the 1016−1019cm−3 range have been carried out. These results show that MOVPE growth is fully compatible with the achievement of highly Al-doped n-type thin films, but also with the growth of materials with low residual doping, which is a crucial parameter to address ZnO p-type doping issues.