The tunnelling properties in metal/diamond-like carbon (DLC)/semiconductor junctions and structural characteristics of thin DLC films produced using different electron beam conditions were studied. We show that under the same electron dose conditions, thicker DLC films were obtained using lower accelerating voltages (2 kV) than when using higher accelerating voltage (20 kV). However, under the settings used the thicker films showed worse insulating performance than the thinner films. We attribute this effect to the variation of tunnelling barrier height in DLC deposited using different accelerating voltages. DLC films with a tunnelling barrier height of up to 3.12 eV were obtained using a 20 kV electron-beam, while only 0.73 eV was achieved for 2 kV DLC films. The X-ray photoemission spectra of the C 1s core level in these films reveal components at 284.4 +/- 0.1 eV and 285 +/- 0.1 eV, which were identified as the sp(2) and sp(3) hybrid forms of carbon. The sp(3)/sp(2) concentration ratio increased with increasing electron beam accelerating voltage. We show how this effect is responsible for the barrier height variation. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.