We analyze the dependence of the interface defect density Dit in amorphous/crystalline silicon (a-Si:H/c-Si) heterojunctions on the microscopic properties of ultrathin (10 nm) undoped a-Si:H passivation layers. It is shown that the hydrogen bonding and network disorder, probed by infrared- and photoelectron spectroscopy, govern the initial Dit and its behavior upon a short thermal treatment at 200 °C. While the initial Dit is determined by the local and nonequilibrated interface structure, the annealed Dit is defined by the bulk a-Si:H network strain. Thus it appears that the equilibrated a-Si:H/c-Si interface does not possess unique electronic properties but is governed by the a-Si:H bulk defects. © 2010 American Institute of Physics.