Hydrogen, oxygen and hydroxyl on porous silicon surface: A joint density-functional perturbation theory and infrared spectroscopy approach

• The density functional perturbation theory is used to study infrared absorption.
• An ordered pore model is used to investigate the oxidation in porous silicon (PSi).
• Infrared transmittance spectra of oxidized PSi freestanding samples are measured.

Based on the density functional perturbation theory (DFPT), infrared absorption spectra of porous silicon are calculated by using an ordered pore model, in which columns of silicon atoms are removed along the [001] direction and dangling bonds are initially saturated with hydrogen atoms. When these atoms on the pore surface are gradually replaced by oxygen ones, the ab-initio infrared absorption spectra reveal oxygen, hydroxyl, and coupled hydrogen–oxygen vibrational modes. In a parallel way, freestanding porous silicon samples were prepared by using electrochemical etching and they were further thermally oxidized in a dry oxygen ambient. Fourier transform infrared spectroscopy was used to investigate the surface modifications caused by oxygen adsorption. In particular, the predicted hydroxyl and oxygen bound to the silicon pore surface are confirmed. Finally, a global analysis of measured transmittance spectra has been performed by means of a combined DFPT and thin-film optics approach.