The fabrication of organic electronic devices involving complex stacks of solution-processable functional materials has proven challenging. Significant material intermixing often occurs as a result of cross-solubility and postdeposition treatments, rendering the realization of even the simplest bilayer architectures rather cumbersome. In this study we investigate the feasibility of a dry transfer printing process for producing abrupt bilayer organic photodiodes (OPDs) and the effect of thermal annealing on the integrity of the bilayer. The process involves the transfer of readily deposited thin films of poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) using a polydimethylsiloxane (PDMS) stamp. Fabricated structures are characterized by means of cross-sectional scanning electron microscopy (SEM), UV/vis absorption spectroscopy, and time-of-flight secondary ion mass spectrometry (TOF-SIMS). Joint consideration of all results unveils abrupt interfaces with no thermal treatment applied and significant material intermixing for samples annealed above 100 °C. The role of the thermally assisted intermixing in determining the performance of complete devices is evaluated through the comparison of J-V characteristics and external quantum efficiencies (EQEs) of identical photodiodes subject to different annealing conditions. It is shown that the performance of such devices approaches the one of bulk heterojunction photodiodes upon thermal annealing at 140 °C for 5 min. Our results demonstrate that transfer printing is a reliable and simple process for the realization of functional multilayers, paving the way for organic electronic devices incorporating complex stacks. It further contributes to a fundamental understanding of material composition within photoactive layers by elucidating the process of thermally assisted intermixing.
Keywords: OPD; P3HT:PCBM; bilayer; interdiffusion; transfer print.