Direct Observation of Conductive Polymer Induced Inversion Layer in n‐Si and Correlation to Solar Cell Performance

Heterojunctions formed by ultrathin conductive polymer [poly(3,4‐ethylenedioxythiophene): poly(styrenesulfonate)—PEDOT:PSS] films and n‐type crystalline silicon are investigated by photoelectron spectroscopy. Large shifts of Si 2p core levels upon PEDOT:PSS deposition provide evidence that a dopant‐free p–n junction, i.e., an inversion layer, is formed within Si. Among the investigated PEDOT:PSS formulations, the largest induced band bending within Si (0.71 eV) is found for PH1000 (high PEDOT content) combined with a wetting agent and the solvent additive dimethyl sulfoxide (DMSO). Without DMSO, the induced band bending is reduced, as is also the case with a PEDOT:PSS formulation with higher PSS content. The interfacial energy level alignment correlates well with the characteristics of PEDOT:PSS/n‐Si solar cells, where high polymer conductivity and sufficient Si‐passivation are also required to achieve high power conversion efficiency. The formation of an inversion layer within n‐Si near the interface with poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) based conductive thin films is evidenced. High power conversion efficiency in solar cells is correlated with a large contact‐induced band bending in Si, high polymer conductivity, and proper Si interfacial passivation.