In this work we propose a detailed investigation of the Al – Si interdiffusion that occurs during the firing process of the Al-Si back contact of silicon based solar cells. The investigation is based on high resolution scanning electron microscopy (SEM) and compositional microanalysis with energy dispersive X-Ray microanalysis (EDX). We have found a dependence of Si precipitation in the Al matrix depending on the microstructure of the Al screen printable paste. We suggest a gettering effect promoted by the larger Al particles lying within the Al paste being able to affect the Al paste resistivity, the Al distribution within the BSF region of the solar cell, thus affecting the solar cell performances and finally the Al paste thermal expansion coefficient. Finally we demonstrate that the presence of the glass frit reduces the surface tension and, homogenizes the diffusion process. Reduction of surface tension decreases the internal pressure and increases the Si interdiffusion in Al.