Recovery of surface conductivity of H-terminated diamond after thermal annealing in vacuum

A unique feature of diamond among other semiconductors is the formation of a high conductive p-type layer which is usually obtained after hydrogen-termination of the surface. It is generally accepted that the appearance of surface conductivity (SC) requires the presence of atmospheric adsorbates. We present a combination of conductivity and spectroscopic measurements dealing with the loss and the formation of SC as a function of annealing in vacuum (temperatures 60-900°C) and exposure to different atmospheres. For temperatures below 190 °C in vacuum the SC decreases by more than five orders of magnitude and comes back to its initial value when the sample is exposed to air. After annealing between 250 and 700 °C exposure to normal atmospheric conditions is no longer sufficient to recover SC, although the H termination is preserved. In this state the SC is fully restored upon air exposure after the surface has been exposed to ozone or oxygen radicals. We propose a model where oxygen-related sites are catalytically involved in the transfer-doping mechanism such that the rate of electron transfer from the diamond into solvated adsorbates is enhanced.