Kesterite (CZTSe) is a promising thin film photovoltaic absorber material due to its composition of more earth abundant materials compared to mature thin film photovoltaic technologies. Up to now, power conversion efficiencies are still lower and its main problem is the low open circuit voltage (Voc). Recently, a novel sintering approach using a nanometric Ge layer showed a large increase in device performance and especially in Voc. In this work, in-depth solar cell characterization as well as Raman and Photoluminescence studies of devices employing different Ge doped CZTSe absorber layers is presented. The main focus is to reveal the beneficial effects of Ge doping and furthermore investigate the interaction of Ge and Na. For low Ge doping an increase in charge carrier concentration is observed, resulting in devices with Voc of 460 mV, which corresponds to Voc deficits (Eg/q–Voc) of 596 mV a value comparable to current record devices. For high Ge amounts admittance spectroscopy measurements identified the appearance of a deep defect which can explain the observed deterioration of solar cell performance. Additional Na provided during crystallization of high Ge doped devices can reduce the density of this deep defect and recover device performance. These results indicate that Na plays an important role in defect passivation and we propose a defect model based in the interaction of group IV elements and Na with Cu vacancies.