Chemical Annealing of Zinc Tetraphenylporphyrin Films: Effects on Film Morphology and Organic Photovoltaic Performance

We present a chemical annealing process for organic thin films. In this process, a thin film of a molecular material, such as zinc tetraphenylporphyrin (ZnTPP), is exposed to a vapor of nitrogen-based ligand (e.g., pyrazine, pz, and triazine, tz), forming a film composed of the metal–ligand complex. Fast and quantitative formation of the complex leads to marked changes in the morphology and optical properties of the film. X-ray diffraction studies show that the chemical annealing process converts amorphous ZnTPP films to crystalline ZnTPP·ligand films, whose porphryin planes lie nearly parallel to the substrate (average deviation is 8° for the ZnTPP·pz film). Organic solar cells were prepared with ZnTPP donor and C₆₀ acceptor layers. Devices were prepared with and without chemical annealing of the ZnTPP layer with a pyrazine ligand. The devices with chemically annealed ZnTPP donor layer show an increase in short-circuit current (<i>J</i>_SC) and fill factor (<i>FF</i>) relative to analogous unannealed devices, presumably because of enhanced exciton diffusion length and improved charge conductivity. The open circuit voltages (<i>V</i>_OC) of the chemically annealed devices are lower than their unannealed counterpart because of enhanced polaron pair recombination at the donor/acceptor heterojunction. A net improvement of 5–20% in efficiency has been achieved, after chemical annealing of ZnTPP films with pyrazine