The detailed characterization of solution‐derived nickel (II) oxide (NiO) hole‐transporting layer (HTL) films and their application in high efficiency organic photovoltaic (OPV) cells is reported. The NiO precursor solution is examined in situ to determine the chemical species present. Coordination complexes of monoethanolamine (MEA) with Ni in ethanol thermally decompose to form non‐stoichiometric NiO. Specifically, the [Ni(MEA)2(OAc)]+ ion is found to be the most prevalent species in the precursor solution. The defect‐induced Ni3+ ion, which is present in non‐stoichiometric NiO and signifies the p‐type conduction of NiO, as well as the dipolar nickel oxyhydroxide (NiOOH) species are confirmed using X‐ray photoelectron spectroscopy. Bulk heterojunction (BHJ) solar cells with a polymer/fullerene photoactive layer blend composed of poly‐dithienogermole‐thienopyrrolodione (pDTG‐TPD) and [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM) are fabricated using these solution‐processed NiO films. The resulting devices show an average power conversion efficiency (PCE) of 7.8%, which is a 15% improvement over devices utilizing a poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) HTL. The enhancement is due to the optical resonance in the solar cell and the hydrophobicity of NiO, which promotes a more homogeneous donor/acceptor morphology in the active layer at the NiO/BHJ interface. Finally, devices incorporating NiO as a HTL are more stable in air than devices using PEDOT:PSS.

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Significant progress in power conversion efficiencies and stabilities of polymer solar cells has been achieved using semiconducting metal oxides as charge extraction interlayers. Both n-and p-type transition metal oxides with good transparency in the visible as well as infrared region make good Ohmic contacts to both donors and acceptors in polymer bulk heterojunction solar cells. Their compatibility with roll-to-roll processing makes them very attractive for low cost manufacturing of polymer solar cells. In this review, we will present the recent results on synthesis and characterization of these metal oxides along with the device performance of the solar cells using these metal oxides as interlayers.

Interface recombination induced by the defect states in zinc‐oxide‐nanoparticle‐based electron extraction layer is reported as a significant loss‐mechanism of photocurrent collection. By choosing appropriate UV–ozone treatment conditions on the zinc oxide layer, inverted polymer solar cells show reduced interface recombination and thus improved power conversion efficiencies of up to 8.1%.

The contact between the n-type interlayer and the donor provides an extra interface for charge dissociation.