Effect of Remote Hydrogen Plasma Treatment on ZnO Single Crystal Surfaces

We have studied the effects of hydrogen plasma treatment on the defect characteristics in single crystal ZnO grown at Eagle-Picher by chemical vapor transport. Depth-dependent cathodoluminescence (CL) spectra, temperature-dependent (9-300 K) and excitation intensity-dependent photoluminescence (PL) spectra reveal significant changes resulting from unannealed exposure of n-type ZnO to a remote hydrogen plasma. Low temperature PL spectra show that this hydrogen exposure effectively suppresses the free-exciton transition and redistributes intensities in the bound-exciton line set and twoelectron satellites with their phonon replicas. The resultant spectra after hydrogenation exhibit a new peak feature at 3.366 eV possibly related to a neutral donor bound exciton. A simple thermal analysis of the activation energy for the 3.366 eV line yields 5-10 meV. Hydrogenation also produces a violet 100 meV-wide peak centered at 3.16 eV. Remote plasma hydrogenation produces similar changes in room-temperature CL spectra: nearband edge emission intensity increases with hydrogenation. Furthermore, this new emission increases with proximity to the free ZnO surfaces, i.e., with decreasing the energy of the incident electron beam from 3.0 down to 0.5 keV. Subsequent annealing at 450 oC completely restores both the PL and CL spectra in the sub-band gap range. The appearance of a new bound-exciton feature at 3.366 eV with H plasma exposure, the near-surface nature of the spectral changes, and the reversibility of spectral features with annealing indicate a direct link between H indiffusion and appearance of a shallow donor. M3.9.1 Mat. Res. Soc. Symp. Proc. Vol. 744 © 2003 Materials Research Society