We present some investigations on the electrical conductivity of two benzene substituted derivatives (m-DNB, benzil) emphasizing the correlation between the molecular structure, purity, structural defects and the particularities of the conduction mechanisms. The influence of inorganic/organic doping on the I-V plots of silicon/wide-gap organic semiconductor/silicon heterostructures has been analysed. The most significant increase in the conductance has been obtained for organic crystalline films of benzil doped with 3 wt.% m-DNB and m-DNB films doped with I wt.% oxine or 10 wt.% resorcinol. The influence of the silicon wafer's properties as resistivity, conduction type and surface processing on the carrier transport properties in these structures has been studied. We have remarked an increase in the conductance of the organic films of m-DNB doped with oxine or resorcinol in heterostructures realized with chemically polished, "n" type single crystal silicon wafers, compared to lapped ones. A special type of conduction mechanism given by a Poole-Frenkel dependence was evidenced in resorcinol doped m-DNB in the low voltages range. (c) 2005 Elsevier B.V. All rights reserved.