The intermediate layer (IL) between glass substrate and silicon plays a significant role in the optimization of multicrystalline liquid phase crystallized silicon thin film solar cells on glass. This study deals with the influence of the IL on the surface condition and the required chemical surface treatment of the crystallized silicon (mc-Si), which is of particular interest for a-Si:H heterojunction thin film solar cells. Two types of IL were investigated: sputtered silicon nitride (SiN) and a layer stack consisting of silicon nitride and silicon oxide (SiN/SiO). X-ray photoelectron spectroscopy measurements revealed the formation of silicon oxynitride (SiOxNy) or silicon oxide (SiO2) layers at the surface of the mc-Si after liquid phase crystallization on SiN or SiN/SiO, respectively. We propose that SiOxNy formation is governed by dissolving nitrogen from the SiN layer in the silicon melt which segregates at the crystallization front during crystallization. This process is successfully hindered, when additional SiO layers are introduced into the IL. In order to achieve solar cell open circuit voltages above 500 mV, a removal of the formed SiOxNy top layer is required using sophisticated cleaning of the crystallized silicon prior to a Si:H deposition. However, solar cells crystallized on SiN/SiO yield high open circuit voltage even when a simple wet chemical surface treatment is applied. The implementation of SiN/SiO intermediate layers facilitates the production of mesa type solar cells with open circuit voltages above 600 mV and a power conversion efficiency of 10%.