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.
Solvent additives provide an effective means to alter the morphology and thereby improve the performance of organic bulk‐heterojunction photovoltaics, although guidelines for selecting an appropriate solvent additive remain relatively unclear. Here, a family of solvent additives spanning a wide range of Hansen solubility parameters is applied to a molecular bulk‐heterojunction system consisting of an isoindigo and thiophene containing oligomer as the electron donor and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PC61BM) as the electron acceptor. Hansen solubility parameters are calculated using the group contribution method and compared with the measured solubilities for use as a screening method in solvent additive selection. The additives are shown to alter the morphologies in a semipredictable manner, with the poorer solvents generally resulting in decreased domain sizes, increased hole mobilities, and improved photovoltaic performance. The additives with larger hydrogen bonding parameters, namely triethylene glycol (TEG) and N‐methyl‐2‐pyrrolidone (NMP), are demonstrated to increase the open circuit voltage by ~0.2 V. Combining a solvent additive observed to increase short circuit current, poly(dimethylsiloxane), with TEG results in an increase in power conversion efficiency from 1.4 to 3.3%.
A double interlayer composed of MoO3 and poly(9,9-dioctylfluorene-co-N-[4-(3-methylpropyl)]-diphenylamine) (TFB) was used as an anode contact for bulk heterojunction polymer solar cells. Using this strategy, photovoltaic cells with poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylene vinylene]: [6,6]-phenyl-C61 butyric acid methyl ester (MDMO-PPV:PCBM) blend as a photoactive layer were fabricated. An enhancement in power conversion efficiency of 53% was observed in cells with a double interlayer compared with cells having a PEDOT: PSS interlayer. The enhancement is attributed to the combined effects of electron blocking and enhanced charge extraction from the photoactive layer to the anode.
The effect of ZnO defects on photoexcited charge carrier recombination and forward induced charge transfer was studied in organic-inorganic bilayer organic heterojunction solar cells. Decreased bimolecular recombination via passivation of ZnO nanopariticle defects resulted in longer carrier lifetime as determined by transient photovoltage (TPV) measurements. It was also found by time-resolved photoluminescence (TRPL) measurements that defect passivation decreased the fluorescence lifetime which indicated higher exciton dissociation efficiency. Through passivation of the ZnO nanoparticles defects, the two loss mechanisms were reduced and the power conversion efficiency (PCE) is significantly enhanced.
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