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A systematical investigation was carried out into the effects of the hole-transporting layer treatment of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) on the performance of planar hybrid n-Si/PEDOT:PSS solar cells. Triton X-100 and ethylene glycol (EG) were chosen to improve the conductivity and surface morphology of the PEDOT:PSS film. It was found that the annealing temperature has a great influence on the PEDOT:PSS material properties and the corresponding device performance. By optimizing the annealing temperature, the conductivity of the PEDOT:PSS film doped with Triton X-100 and EG could be enhanced by a factor of more than three orders. And the corresponding device also shows record power conversion efficiency as high as 14.5% with an open circuit voltage of 0.627 V, a short circuit current of 32.6 mA/cm2, and a fill factor of 70.7%.