Thermal characterization of semiconducting polymer bulk heterojunctions
Date
2016
Authors
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Publisher
University of Delaware
Abstract
Polymer semiconductors are intriguing due to their potential use in flexible electronics. Poly (3-hexylthiophene) (P3HT)—a very common polymer in this field—is semicrystalline and it is known that crystalline P3HT has a higher hole mobility than amorphous P3HT. Quantifying each fraction in the bulk and thin film states is therefore crucial to understanding its performance in transistor and other applications. In polymer solar cells, it acts as an electron donor and is typically mixed with the nanoparticle-like molecule, phenyl-C61-butyric acid methyl ester (PCBM)—an electron acceptor—in a thin film morphology termed a bulk heterojunction (BHJ). The structural hierarchy within the bulk heterojunction is complicated and its characterization, with a focus on P3HT morphology, is the topic of this dissertation. ☐ Calorimetry can play an important role in the elucidation of P3HT morphology with quantitative analysis of the crystalline and amorphous fractions present in the material. This was demonstrated by employing differential scanning calorimetry (DSC) to obtain the enthalpy of fusion of 100% crystalline P3HT (42.9 J/g) using oligomeric P3HT measurements. The more sensitive temperature modulated DSC (TMDSC) was then used to examine the glass transition of P3HT and the crystalline, mobile amorphous and rigid amorphous phases were quantified. The presence of these phases can play a large role in understanding the charge transfer process in polymer semiconductors. ☐ BHJ thin films of 50 wt.% PCBM were then analyzed and a polymer crystallinity of 30% was found after thermal annealing from initially non-crystalline polymer material. With assistance from previously acquired small angle neutron scattering data, a thorough analysis of the entire BHJ morphology was accomplished. A surprisingly large rigid amorphous polymer phase is present in the BHJ which could be located at the P3HT/PCBM interface, affecting charge transfer. ☐ Finally, interlayer diffusion of PCBM was examined using neutron reflectivity. By measuring the diffusion between bilayers it was found that up to 12% PCBM is able to diffuse into the PEDOT:PSS electron blocking polymer layer. The possible mixing of these two materials is typically ignored but this study suggests that more attention should be paid to diffusion across the PEDOT:PSS/BHJ interface.