We explore the (near-)interface structure of amorphous/crystalline silicon (a-Si:H/c-Si) heterojunctions as employed in high-efficiency heterojunction solar cells. We make use of secondary-ion-mass-spectroscopy profiles and minority carrier lifetime measurements taken on undoped deuterated amorphous silicon [(i)a-Si:D] layers deposited on c-Si from deuterated silane at identical conditions as the hydrogenated layers we have analyzed previously [T. F. Schulze et al., Appl. Phys. Lett. 96 (2010) 252102]. We briefly discuss the implications of the local interface structure for the c-Si surface passivation as well as for the heterojunction band offsets, and identify a route towards optimization of (i)a-Si:H layers as passivating buffers in a-Si:H/c-Si high-efficiency heterojunction solar cells. © 2012 Elsevier B.V. All rights reserved.