Electrical and optical properties of zinc oxide for scintillator applications

Abstract

Zinc oxide (ZnO) is a wide-band-gap semiconductor suitable for many optical and optoelectronic applications. Among these is to use single crystal, powder, or ceramic forms of ZnO as a fast UV scintillator. In this work, the electrical and optical properties of ZnO were studied using photoluminescence, X-ray-induced luminescence, optical absorption, and Hall Effect techniques. This study included single crystal ZnO and ZnO:Ga samples grown from high-pressure-melt (HPM), seeded chemical-vapor-transport (SCVT), and hydrothermal (HYD) techniques; powder samples synthesized using both solution and solid-state processes, and purchased from different commercial sources; and ceramic samples prepared by hot-uni-axial-pressing and spark-plasma-sintering methods. Temperature-dependent PL and Hall measurements were combined to establish the luminescence origins in the n-type ZnO and ZnO:Ga single crystals. Based on a PL line-shape analysis, including band-gap renormalization, the direct (e,h) transition is the main luminescent channel in highly n-type ZnO:Ga, while FX and FX-LO recombinations are responsible for the UV PL from as-grown ZnO. An intrinsic mobility limit for n-type ZnO was established by including three major phonon-scattering mechanisms. Analysis of Hall data from single-crystal samples including both neutral- and ionized-impurity scatterings provided donor and acceptor concentrations and energy levels. High n-type single-crystal ZnO samples prepared either by Ga doping and co-doping, or by after-growth treatments, were also studied. Absorption and reflectance data were used to obtain free carrier concentrations from the Ga-doped and co-doped crystals, and it was found that several samples with n ∼ high-10¹⁸ to low-10¹⁹ cm ^-3 had optimum UV luminescence. Anneal treatments in reducing atmospheres increased free carrier concentrations in HPM and HYD samples, but an induced absorption band due to oxygen vacancies limited the UV emission from these samples. PL and X-ray-induced luminescence studies on powder ZnO:Ga samples demonstrated that high Ga-doping levels and H-anneal treatments can improve UV emission, while impurities such as Cu and Li enhance the lower energy visible emissions and affect the UV output. For ceramic forms of ZnO, reduction of scattering losses remains as the main challenge for improved scintillation.