Silicon heterojunction solar cells critically depend on the detailed properties of their amorphous/crystalline silicon interfaces. We report here on the use of attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy to gain precise insight into the vibrational properties of the surfaces and ultrathin layers present in such solar cells. We fabricate ATR prisms from standard silicon wafers similar to those used for device fabrication. In this fashion, we acquire very-high sensitivity FTIR information on device-relevant structures. Our method has no requirement for minimum layer thickness, enabling the study of the impact of the different fabrication process steps on the film microstructure. We discuss the necessary requirements for the method implementation and give a comprehensive overview of all observed vibration modes. In particular, we study vibrational signatures of Si-H-X, Si-H-X(SiYOZ), B-H, hydroxyl groups, and hydrocarbons on the Si(111) surface. We observe subtle effects in the evolution of the chemical state of the surface during sample storage and process-related wafer handling and discuss their effect on the electronic properties of the involved interfaces. (C) 2015 AIP Publishing LLC.