Abstract
We have developed photoelectrochemical cells with rectifying junctions between n‐Si electrodes and thin film solvent free polymer solid electrolytes based on poly(ethylene oxide). We describe various surface modifications applied to the n‐Si electrode which overcome a high activation energy barrier for efficient charge transfer to redox ions in the polymer solid electrolytes. We show that the efficiency of the present cells is limited by a high surface recombination velocity associated with surface states of the n‐Si.