High conversion efﬁciency (η) values have been obtained from modiﬁed CuS ﬁlm electrodes electrochemically
deposited onto Glass/FTO. The modiﬁcation involved pre-annealing the ﬁlm followed by
coating with tetra(-4-pyridyl)porphyrinato manganese (MnTPyP
) ions embedded inside a polyethylene
(PE) matrix. The Glass/FTO/CuS/MnTPyP/PE electrodes exhibited enhanced photo-electrochemical (PEC)
characteristics under solar simulated illumination (5.6 mW/cm
) in aqueous media, compared to the
as-prepared Glass/FTO/CuS ﬁlms which showed no PEC activity. Up to 17.4% efﬁciency and 85% ﬁll factor
(FF) values were obtained from the modiﬁed ﬁlm electrodes. Such characteristics have not been widely
known for metal chalcogenide based ﬁlm electrodes before. Different pre-annealing temperatures were
attempted and the 250 °C temperature, followed by quenching, showed favorable results. Different
aqueous redox couples were studied and the environmentally safe FeCl
aqueous system showed
highest PEC characteristics. Effect of pre-annealing on ﬁlm electrode characteristics is discussed. The
MnTPyP/PE matrix behaves as charge transfer catalyst for the holes across the CuS ﬁlm/liquid junction.
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