A study of H and D doped ZnO epitaxial films grown by pulsed laser deposition

Abstract

We examine the crystal structure and electrical and optical properties of ZnO epitaxial films grown by pulsed laser deposition in a H2 or D2 ambient. n-type electrical conductivity is enhanced by three orders of magnitude as a result of growing in H2 (D2) compared to ZnO films grown in O2. Hall effect measurements reveal very small carrier activation energies and carrier concentrations in the mid-1018 cm−3 range. Optical absorption measurements show that the enhanced conductivity is not a result of ZnO reduction and interstitial Zn formation. Photoluminescence spectra suggest excitonic emission associated with exciton-hydrogen donor complex formation and show no evidence for midgap emission resulting from defects. We have modeled the transport properties of H (D) doped ZnO films using variable range hopping and surface layer conductivity models, but our data do not fit well with these models. Rather, it appears that growth in H2 (D2) promotes the formation of an exceedingly shallow donor state not seen in ZnO crystals annealed in H2 after growth. This new state may be associated with H (D) substitution at O sites in the lattice.