Ge-rich GeSbTe N-doped alloys present a solution for the reliability and thermal stability requirements of Phase Change Memories for embedded non-volatile memory automotive applications. The thermal performance of these memories is defined by the optimization of crystallization temperature, kinetics and thermal properties of materials and interfaces. In this work, we study the structural evolution and crystallization temperature of Ge-rich GeSbTe N-doped alloy from amorphous phase to complete crystallization by Raman spectroscopy. We highlight the beginning of crystallization process by Ge crystallization, followed by crystallization of both GeTe and SbTe related structures. Further, the sensitivity of the vibrational modes present in this ternary chalcogenide alloy to temperature and power is examined to identify potential thermometers. Finally, we present the working principle of Raman thermometry to extract the thermal conductivity aided by finite-element calculations and report the thermal conductivity of Ge-rich GeSbTe N-doped alloy.