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Thin films of hydrogenated amorphous carbon (a-C:H) deposited by radio frequency plasma-enhanced chemical vapour deposition (rf-PECVD) have been studied for various applications. An interesting property of these films is their high breakdown strength (107 Vcm-1). This property of a-C:H can be exploited in high breakdown heterostructure diodes or as passivation layers and insulator layers in MIS devices. Reports on the applications of a-C:H/Si diodes exist in the literature. Diodes in which the a-C:H films have been deposited by rf-PECVD, have been reported only once. In this article the diodes produced reportedly failed to exhibit reproducible I-V characteristics under high voltage stress. We have investigated the process dependence of structural and electrical properties of rf-PECVD a-C:H films deposited at room temperature from a CH4/Ar gas mixture (at a pressure of 100 mTorr) using a capacitively coupled rf-PECVD. We observe a clear correlation between the dc-self bias and the rectification ratio of a-C:H/Si heterojunction diodes. Optimised diodes show rectification ratios upto 104 and a stable reverse breakdown voltage, typically around 850 V. I-V and C-V measurements show no evidence of hystersis. Scanning Electron Microscopy was carried out to determine the quality of the films deposited. Micro-Raman analysis was used to estimate the ID/IG ratio in the films deposited under different dc-self bias., Comment: 6 pages, 4 figures