We investigated hybrid inorganic-organic solar cells combining monocrystalline
n-type silicon (n- Si) and a highly conductive polymer
poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS). The
build-in potential, photo- and dark saturation current at this hybrid
interface are monitored for varying n-Si doping concentrations. We corroborate
that a high build-in potential forms at the hybrid junction leading to strong
inversion of the n-Si surface. By extracting work function and valence band
edge of the polymer from ultraviolet photoelectron spectroscopy, a band
diagram of the hybrid n-Si/PEDOT:PSS heterojunction is presented. The current-
voltage characteristics were analyzed using Schottky and abrupt pn-junction
models. The magnitude as well as the dependence of dark saturation current on
n-Si doping concentration proves that the transport is governed by diffusion
of minority charge carriers in the n-Si and not by thermionic emission of
majorities over a Schottky barrier. This leads to a comprehensive explanation
of the high observed open-circuit voltages of up to 634 mV connected to high
conversion efficiency of almost 14%, even for simple planar device structures
without antireflection coating or optimized contacts. The presented work
clearly shows that PEDOT:PSS forms a hybrid heterojunction with n-Si behaving
similar to a conventional pn-junction and not, like commonly assumed, a
Schottky junction