N-doped homo-epitaxial GaN samples grown on freestanding GaN substrates have been investigated by micro-Raman spectroscopy. Quantitative analysis of the E2h and the A1(LO) modes’ behavior has been performed while intentionally increasing the carrier density using silicon doping. We noticed that as the carrier concentration increases up to 1.8 × 1018 cm−3, the E2h mode remains unchanged. On the other hand, when the doping gets higher, the A1(LO) position shifts to a higher frequency range, its width becomes larger, and its intensity drastically diminishes. This change in the A1(LO) behavior is due to its interaction and its coupling with the free negative charge carriers. Furthermore, we calibrated the A1(LO) frequency position shift as a function of the n-carrier concentration. We found out that for low n doping, the change in the A1(LO) position can be considered as a linear variation while in the overall doping range, a sigmoid growth trend with a Boltzmann fit can be tentatively applied to describe the A1(LO) position shift. This calibration curve can also be used to describe the coupling strength between the carriers and the A1(LO) phonon. Eventually, this study shows that micro-Raman spectroscopy is a powerful non-destructive tool to probe the doping concentration and the crystalline quality of GaN material with a microscopic spatial resolution.