We report the fabrication of high performance organic solar cells by spray‐coating the photoactive layer in air. The photovoltaic blends consist of a blend of carbazole and benzothiadiazole based donor–acceptor copolymers and the fullerene derivative PC70BM. Here, we formulate a number of photovoltaic inks using a range of solvent systems that we show can all be deposited by spray casting. We use a range of techniques to characterize the structure of such films, and show that spray‐cast films have comparable surface roughness to spin‐cast films and that vertical stratification that occurs during film drying reduces the concentration of PCBM towards the underlying PEDOT:PSS interface. We also show that the active layer thickness and the drying kinetics can be tuned through control of the substrate temperature. High power conversion efficiencies of 4.3%, 4.5% and 4.6% were obtained for solar cells made from a blend of PC70BM with the carbazole‐based co‐polymers PCDTBT, P2 and P1. By applying a low temperature anneal after the deposition of the cathode, the efficiency of spray‐cast solar‐cells based on a P2:PC70BM blend is increased to 5.0%. Spray coating holds significant promise as a technique capable of fabricating large‐area, high performance organic solar cells in air.

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The preparation of anthracene-based low band gap conjugated polymers comprising 2,6-linked anthracene and dithienyl-benzo[c][1,2,5]thiadiazole or dibithiophenyl-benzo[c][1,2,5]thiadiazole alternate repeat units is presented. The photophysical, electrochemical and photovoltaic properties of the polymers in bulk heterojunction solar cells using PC(71)BM as an acceptor are discussed.

Electron microscopy has been used to study the degradation of organic solar cells when exposed to humid air. Devices with various different combinations of commonly used organic solar cell hole transport layers and cathode materials have been investigated. In this way the ingress of water and the effect it has on devices could be studied. It was found that calcium and aluminum in the cathode both react with water, causing voids and delamination within the device. The use of poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) was found to increase the degradation by easing water ingress into the device. Replacing these materials removed these degradation features. © 2015 The Authors. Journal of Polymer Science Part B: Polymer Physics published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 216–224

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