A temperature-dependent study of the near-infrared (NIR) responsivity of Ge-on-Si photodiodes is presented. The diodes, formed as n-Ge islands within oxide windows on n-Si and capped with Ga and B layers (PureGaB), exhibit low dark current of ∼2 × 10−13 A/µm2 and broadband responsivity. Temperature-dependent measurements reveal an inherent potential barrier at the low-doped n-Ge on the n-Si heterointerface. This leads to a decrease in responsivity with decreasing temperatures for wavelengths above 1100 nm. The Al-migration process along the Ge-Si interface, associated with the sidewall passivation and found to be a means of reducing dark current, increases the barrier height. Irrespective of the barrier height, room-temperature responsivity is fully recovered by applying a reverse bias to lower the interface barrier. In the devices with the highest barrier, the responsivity at 1310 nm increased from 4.8 to 164 mA/W, at 0 V and 18 V reverse bias, respectively. An additional increase in maximum responsivity at 1550 nm is attributed to Al-sidewall passivation leading to a measured responsivity of 126.4 mA/W at 18 V reverse bias.