To realize organic solar cells with high performance, we developed a novel way of stable n-doping using cationic dyes in electron transport materials. In our approach, the volatile donors are created in-situ from stable precursor compounds. Using the cationic dye pyronin B (PyB) as a model precursor, we carried out conductivity and field effect measurements to characterize the properties of doped naphtalene tetracarboxylic dianhydride (NTCDA) thin film. The results show a strong increase in n-type conductivity. Combined FTIR, UV/VIS/NIR and mass spectroscopic measurements suggest the formation of leuco pyronin B during sublimation of pyronin B chloride, and a subsequent charge transfer between dopant and matrix providing free electrons, which increase the n-type conductivity.