PNNL

Abstract

Zinc oxide (ZnO) adopts wurtzite structure and possesses a direct wide band gap (Eg ~ 3.3 eV at 300 K), similar to that of GaN (Eg ~ 3.4 eV at 300 K), which enables ZnO as an alternative candidate to replace GaN for use in optoelectronic devices. The present controversy is centered at the microscopic origin of the “native donors”, particularly after ab initio calculations by Van de Walle, which indicate that hydrogen is soluble in ZnO at the interstitial sites, effectively forming a donor level just below the conduction band in ZnO. Hence, the origin of n type conductivity in ZnO is proposed due to the presence of hydrogen. Electron paramagnetic resonance and spectroscopic observations of muons provide experimental evidence of hydrogen presence in ZnO. Whereas, Look et al. suggests that the complex of zinc interstitial and nitrogen defect is a stronger candidate for donor than hydrogen interstitials under N ambient. Hydrogen-oxygen complex is claimed to be stable even at T > 1000°C in the hydrothermally synthesized ZnO. Therefore, the thermodynamic nature of hydrogen characteristics remains controversial, particularly its role on resident defects. In this letter, in situ temperature dependent solid state 1H magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy is employed to probe the local chemical environments of hydrogen in ZnO nanorods. To best knowledge of ours, this is the first time that the presence of hydrogen, its concentration, and local transport dynamics are directly chemically determined. Moreover, in situ NMR allows a new approach to investigate the absorption and desorption of protons from different sites on the ZnO nanorods, thus study of site-specific proton dynamics in ZnO becomes feasible.