Although p-type organic mixed ionic electronic conductors (OMIECs) are susceptible to oxidation, it has not yet been considered as to whether oxygen could behave as an uncontrolled p-dopant. Here, oxygen dissolved in solvents is shown to be behave as a p-dopant, that fills traps to enable more effective electrochemical doping in OMIECs and organic electrochemical transistors (OECTs). Yet the presence of oxygen is also known to jeopardize OECT stability. A two-step strategy is introduced to solve this contradictory problem, where first the solvent is degassed, and second the OMIEC is doped in a controlled manner using a chemical dopant. This strategy increases on-off ratio, tunes the threshold voltage, and enhances the transconductance, mobility and the µC* product, while having a remarkable impact on both p-type and n-type OECT stability. This simple solution-processing technique is easily implemented, low-cost, and highly effective in an oxygen-rich environment. The data herein suggests that combining chemical doping with solvent degassing could be a broadly applicable technique to improve essential criteria needed to realize organic bioelectronics and more complex OMIEC circuitry
The absorption of a photon by Organic Semiconductors (OSCs) results in the formation of a bound electron-hole pair quasiparticle or Frenkel Exciton. The energy required to separate an exciton into noninteracting electron and hole, Exciton Binding Energy (Eb), is a critical parameter for the purpose of improving the efficiency of optoelectronic devices such as solar cells and light emitting diodes. In the last two decade there have been many efforts to measure the Eb of OSCs using different techniques. However, there are discrepancies in the literature and the reported values are scattered over a large range between a few meV to 1.5eV, even for a specific material. Eb of Frenkel excitons can be estimated as the difference between the transport (Eg) and the optical gap (Eopt), a traditional definition borrowed from the language of Wannier Exciton in inorganic SCs. Here, we explore the Eb of different variants of PBnDT-FTAZ polymer. We focus on the two most common methods used to measure Eg: combination of Ultraviolet Photoelectron Spectroscopy and Inversed Photoelectron Spectroscopy (UPS-IPES) and Solid-State Cyclic Voltammetry (CV). We show that Eb measured by the abovementioned methods are not consistent or correlated with each other. The Eg measured by UPS-IPES technique is comparable with (or even smaller than) Eopt leading to small Eb. On the other hand, CV usually measures larger Eg compared to the Eopt resulting in larger values of Eb that are scattered between 200meV-1eV depending on the molecular structure of the materials. This discrepancy is the result of lack of both an exclusive theoretical and a functional definition of Eb that includes the relaxation effects, an important characteristic of Frenkel excitons. Moreover, due to the nature of each measurement method, they might measure different parameters than the actual properties of the bulk in a photovoltaic device. Our results elucidate the current conundrum on determination of Eb in OSCs and emphasize the importance of establishing standard theoretical and practical guidelines on how to properly estimate Eb.
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