Evolution of porous silicon crystal structure during storage in ambient air

Both double- and triple- crystal X-ray diffraction techniques (X-ray DCD and TCD techniques) together with transmission electron microscopy (TEM) were employed for the investigation of structural changes in porous silicon (PS) layers during prolonged periods (up to 6800 hours) of their storage in ambient air. Apart from the Bragg reflection from the Si substrate, the diffraction pattern contains an additional maximum caused by the presence of the PS layer with an increased lattice parameter. The position of this peak shifts to smaller Bragg angles and its intensity decreases as the time of storage in air increases. In addition, the profiles of such peaks become clearly asymmetric. In this case, Gaussian curves were used to reach a fit to the experimental X-ray rocking curves. All samples were biaxially bent due to compressive stresses that arise as soon as 10 min after electrochemical process. The values of lattice strains along the surface normal (Δd/d)_⊥ and lateral deformation (Δd/d)_|| were estimated to be ~ +10⁻³, ~ −10⁻⁵ respectively. The analysis of diffraction curve evolution shows a gradual destruction of the crystal lattice caused by the air oxidation process.