We studied lateral silicon p-i-n junctions, doped with phosphorus and boron, regarding charge sensing feasibility. In order to examine the detection capabilities and underlying mechanism, we used in a complementary way two measurement techniques. First, we employed a semiconductor parameter analyzer to measure I−V characteristics at a low temperature, for reverse and forward bias conditions. In both regimes, we systematically detected Random Telegraph Signal. Secondly, using a Low Temperature Kelvin Probe Force Microscope, we measured surface electronic potentials. Both p-i-n junction interfaces, p-i and i-n, were observed as regions of a dynamic behaviour, with characteristic time-dependent electronic potential fluctuations. Those fluctuations are due to single charge capture/emission events. We found analytically that the obtained data could be explained by a model of two-dimensional p-n junction and phosphorus-boron interaction at the edge of depletion region. The results of complementary measurements and analysis presented in this research, supported also by the previous reports, provide fundamental insight into the charge sensing mechanism utilizing emergence of individual dopants.