For ambient radio-frequency (RF) energy harvesting, the available power levels are quite low, and it is highly desirable that the rectifying diodes do not consume any power at all. Contrary to semiconducting diodes, a tunnelling diode – also known as a metal-insulator-metal (MIM) diode – can provide zero-bias rectification, provided the two metals have different work functions. This could result in a complete passive rectenna system. Despite great potential, MIM diodes have not been investigated much in the GHz-frequency regime due to challenging nano-fabrication requirements. In this work, we investigate zero-bias MIM diodes for RF energy-harvesting applications. We studied the surface roughness issue for the bottom metal of the MIM diode for various deposition techniques such as sputtering, atomic layer deposition (ALD) and electron-beam (e-beam) evaporation for crystalline metals as well as for an amorphous alloy, namely ZrCuAlNi. A surface roughness of sub-1nm has been achieved for both the crystalline metals as well as the amorphous alloy, which is vital for the reliable operation of the MIM diode. An MIM diode comprising of a Ti-ZnO-Pt combination yields a zero-bias responsivity of 0.25V−1 and a dynamic resistance of 1200Ω. Complete RF characterisation has been performed by integrating the MIM diode with a coplanar waveguide transmission line. The input impedance varies from 100Ω to 50Ω in the frequency range of between 2GHz and 10GHz, which can be easily matched to typical antenna impedances in this frequency range. Finally, a rectified DC voltage of 4.7mV is obtained for an incoming RF power of 0.4W at zero bias. These preliminary results of zero-bias rectification indicate that complete, passive rectennas (a rectifier and antenna combination) are feasible with further optimisation of MIM devices.